KR20220085560A - Modified conjugated diene-based polymer, method of preparing thereof and rubber composition comprising the same - Google Patents

Abstract

The present invention relates to a modified conjugated diene-based polymer having excellent filler affinity, a method for preparing the same, and a rubber composition comprising the same, comprising: a repeating unit derived from a conjugated diene-based monomer; Provided are a modified conjugated diene-based polymer including a functional group derived from a sulfamoylfluoride group-containing compound represented by Formula 1, a method for preparing the same, and a rubber composition including the same.

Description

Modified conjugated diene-based polymer, manufacturing method thereof, and rubber composition comprising the same

The present invention relates to a modified conjugated diene-based polymer having excellent filler affinity, a method for preparing the same, 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 rolling 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 is used by bonding or modifying the chain ends of the formed polymer using various modifiers. 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, the polymerization of SBR or BR can be carried out by batch or continuous polymerization. In the case of batch polymerization, the molecular weight distribution of the prepared polymer is narrow, which has an advantage in terms of improving physical properties, but the productivity is low and , there is a problem of poor processability, and in the case of continuous polymerization, the polymerization is continuously performed and thus the productivity is excellent, and there are advantages in terms of processability improvement, but there is a problem in that the physical properties are poor because the molecular weight distribution is wide. Accordingly, there is a continuous demand for research to improve all of the productivity, processability, and physical properties at the time of manufacturing SBR or BR.

US 4397994 A

The present invention has been devised to solve the problems of the prior art, and includes a functional group derived from a compound containing a sulfamoyl fluoride group represented by Chemical Formula 1 in the molecule, and has excellent filler affinity and improved compounding properties. It aims to provide a polymer.

Another object of the present invention is to provide a method for producing the modified conjugated diene-based polymer.

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

In order to solve the above problems, the present invention is a repeating unit derived from a conjugated diene-based monomer; And it provides a modified conjugated diene-based polymer comprising a functional group derived from a compound containing a sulfamoyl fluoride group represented by the following formula (1):

[Formula 1]

In Formula 1,

R ₁ , R ₂ and R ₄ are each independently an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or —SO ₂ A (here In, A is F or Cl), or R ₁ and R ₂ are connected to each other to form a saturated or unsaturated heterocyclic group having 3 to 10 carbon atoms together with N, or R ₂ and R ₄ are connected to each other to form N and together with R ₃ to form a heterocyclic group having 3 to 10 carbon atoms,

R ₃ is an alkylene group having 1 to 10 carbon atoms,

a is 0 or 1.

In addition, the present invention comprises the steps of preparing an active polymer by 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 (S1); And it provides a method for producing the modified conjugated diene-based polymer comprising the step (S2) of reacting or coupling the active polymer with a sulfamoylfluoride group-containing compound represented by the following formula (1):

[Formula 1]

In Formula 1,

R ₁ , R ₂ and R ₄ are each independently an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or —SO ₂ A (here In, A is F or Cl), or R ₁ and R ₂ are connected to each other to form a saturated or unsaturated heterocyclic group having 3 to 10 carbon atoms together with N, or R ₂ and R ₄ are connected to each other to form N and together with R ₃ to form a heterocyclic group having 3 to 10 carbon atoms,

R ₃ is an alkylene group having 1 to 10 carbon atoms,

a is 0 or 1.

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 may include a functional group derived from a sulfamoylfluoride group-containing compound represented by Formula 1, and may have excellent filler affinity, and thus may have excellent compounding properties when blended with a filler.

In addition, the method for producing a modified conjugated diene-based polymer according to the present invention comprises the step of preparing an active polymer, and reacting or coupling the active polymer with a sulfamoylfluoride group-containing compound represented by Formula 1, whereby the sulfamoyl A modified conjugated diene-based polymer having excellent filler affinity can be easily prepared by easily introducing a functional group derived from a fluoride group-containing compound into the polymer molecule.

In addition, the rubber composition according to the present invention has excellent compounding properties including the modified conjugated diene-based polymer, and has excellent viscoelastic properties such as wet road resistance and rolling resistance, as well as excellent tensile properties and abrasion resistance.

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 present specification and claims should not be construed as being limited to ordinary or dictionary meanings, and the inventor may properly define the concept of the term in order to best describe his invention. Based on the principle that there is, it should be interpreted as meaning and concept consistent with the technical idea of the present invention.

Definition of Terms

The term 'substitution' used in the present invention may mean that hydrogen of a functional group, atomic group, or compound is substituted with a specific substituent, and when hydrogen of a functional group, atomic group, or compound is substituted with a specific substituent, the functional group, atomic group, or compound is present One or two or more plural substituents may be present depending on the number of hydrogens to be used. In addition, when a plurality of substituents exist, each substituent may be the same as or different from each other.

The term 'alkyl group' used in the present invention may mean a monovalent aliphatic saturated hydrocarbon, and linear alkyl groups such as methyl, ethyl, propyl and butyl, and isopropyl, sec-butyl) , may include all branched alkyl groups such as tert-butyl and neopentyl.

The term 'cycloalkyl group' used in the present invention may mean a cyclic saturated hydrocarbon.

The term 'aryl group' used in the present invention 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. ) may mean including all of them.

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

The terms 'derived unit' and 'derived functional group' used in the present invention may indicate a component, structure, or substance itself derived from a substance.

Modified conjugated diene-based polymer

The present invention provides a modified conjugated diene-based polymer having excellent filler affinity, and excellent compounding processability and compounding properties when compounded with a filler.

The modified conjugated diene-based polymer according to an embodiment of the present invention includes a repeating unit derived from a conjugated diene-based monomer; and a functional group derived from a sulfamoylfluoride group-containing compound represented by the following formula (1).

[Formula 1]

In Formula 1,

R ₁ , R ₂ and R ₄ are each independently an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or —SO ₂ A (here In, A is F or Cl), or R ₁ and R ₂ are connected to each other to form a saturated or unsaturated heterocyclic group having 3 to 10 carbon atoms together with N, or R ₂ and R ₄ are connected to each other to form N and together with R ₃ to form a heterocyclic group having 3 to 10 carbon atoms,

R ₃ is an alkylene group having 1 to 10 carbon atoms,

a is 0 or 1.

According to an embodiment of the present invention, the modified conjugated diene-based polymer may include a repeating unit derived from a conjugated diene-based monomer and a functional group derived from a sulfamoylfluoride group-containing compound represented by Formula 1, wherein the conjugated diene The repeating unit derived from the monomer-based monomer may mean a repeating unit formed during polymerization of the conjugated diene-based monomer, and the functional group derived from the sulfamoylfluoride group-containing compound represented by Formula 1 above is a polymer comprising a repeating unit derived from the conjugated diene-based monomer. It may be a functional group derived from a sulfamoyl fluoride group-containing compound represented by Formula 1 present in the chain, and a functional group derived from a sulfamoyl fluoride group-containing compound represented by Formula 1 may be present at at least one terminal of the polymer chain. can

In addition, according to another embodiment of the present invention, the modified conjugated diene-based polymer may further include a repeating unit derived from an aromatic vinyl-based monomer, and in this case, the modified conjugated diene-based polymer is a repeating unit derived from a conjugated diene-based monomer; It may be a copolymer including a repeating unit derived from an aromatic vinyl-based monomer and a functional group derived from a compound having a sulfamoyl fluoride group represented by Formula 1. Here, the repeating unit derived from the aromatic vinyl-based monomer may mean a repeating unit formed during polymerization of the aromatic vinyl-based monomer.

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 It may be at least one selected from the group consisting of -phenyl-1,3-butadiene and 2-halo-1,3-butadiene (halo means a halogen atom).

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)-α-methylstyrene) at least one selected from the group consisting of can

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 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 to 1% by weight of a repeating unit derived from the diene-based monomer, more than 0% by weight to 0.1% by weight, It may contain more than 0 wt% to 0.01 wt%, or more than 0 wt% to 0.001 wt%, and has the effect of preventing gel formation within this range.

According to an embodiment of the present invention, when the modified conjugated diene-based polymer is a copolymer, the copolymer may be a random copolymer, and in this case, a good balance between physical properties is obtained. The random copolymer may mean that repeating units constituting the copolymer are disorderly arranged.

The modified conjugated diene-based polymer according to an embodiment of the present invention is prepared by the manufacturing method described below comprising reacting the active polymer with a sulfamoylfluoride group-containing compound represented by Chemical Formula 1, wherein Since the represented sulfamoylfluoride group-containing compound has a number of reactive active sites capable of reacting with the active polymer, the repeating unit derived from the conjugated diene monomer of the active polymer or the repeating unit derived from the conjugated diene monomer and the aromatic vinyl monomer derived from the active polymer By reacting or coupling with a plurality of polymer chain active sites composed of repeating units, a filler affinity functional group in the polymer can be easily introduced, and as a result, excellent filler affinity properties can be exhibited.

For example, in Formula 1, a is 0, and R ₁ and R ₂ are each independently an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, or a cycloalkyl group having 6 to 12 carbon atoms. An aryl group, or —SO ₂ A (herein, A is F or Cl), or R ₁ and R ₂ may be connected to each other to form an unsaturated heterocyclic group having 3 to 6 carbon atoms together with N.

In another example, in Formula 1, a is 1, R ₁ is -SO ₂ A (herein, A is F or Cl), R ₂ and R ₄ are connected to each other to have 3 carbon atoms together with N and R ₃ It may be to form a heterocyclic group of 6 to.

As another example, the sulfamoylfluoride group-containing compound represented by Formula 1 may be at least one selected from compounds represented by Formulas 1-1 to 1-5 below.

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

.

.

In addition, the modified conjugated diene-based polymer according to an embodiment of the present invention has a weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) of 300,000 g/mol to 3,000,000 g/mol, 400,000 It may be g/mol to 2,000,000 g/mol or 500,000 to 1,000,000 g/mol, and within this range, the abrasion resistance of the modified conjugated diene-based polymer may be excellent.

On the other hand, the modified conjugated diene-based polymer may have a number average molecular weight (Mn) of 400,000 g/mol to 2,000,000 g/mol, 500,000 g/mol to 1,500,000 g/mol, or 600,000 g/mol to 1,000,000 g/mol, The molecular weight distribution (PDI; MWD; Mw/Mn) may be 1.0 or more and 5.0 or less, or 1.0 or more and 3.0 or less, while having a number average molecular weight and a weight average molecular weight in the above range, and in this case, there is an excellent effect of balance between each physical property .

As another example, the modified conjugated diene-based polymer may have a Mooney viscosity at 100° C. of 30 or more, 30 to 150, or 40 to 140.

When it has a weight average molecular weight in the above-mentioned range and has a Mooney viscosity in the above range, a balance between physical properties is excellent and abrasion resistance can be greatly improved.

Here, the Mooney viscosity was 27±3 g after leaving the polymer at room temperature (23±5°C) for 30 minutes or more at 100°C and a rotor speed of 2±0.02 rpm using a large rotor of Alpha Technologies MV2000. It may be measured while taking a sample, filling it in the die cavity, and applying a torque by operating a platen. In addition, after measuring the Mooney viscosity, the Mooney stress relaxation rate was measured by measuring the slope value of the change in Mooney viscosity appearing when the torque was released, and an absolute value thereof was used as the Mooney stress relaxation ratio.

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 80 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 manufacturing method according to an embodiment of the present invention comprises the steps of preparing an active polymer by 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 (S1); and reacting or coupling the active polymer with a sulfamoylfluoride group-containing compound represented by Formula 1 below (S2).

[Formula 1]

In Formula 1, R ₁ to R ₄ and a are as defined above.

In addition, specific descriptions of the conjugated diene-based monomer, the aromatic vinyl-based monomer, and the sulfamoylfluoride group-containing compound represented by Formula 1 are the same as those described above.

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.

In addition, according to an embodiment of the present invention, the polymerization initiator may be an organometallic compound, and the organometallic compound is not particularly limited, for example, methyllithium, ethyllithium, propyllithium, isopropyllithium, n- Butyllithium, s-butyllithium, t-butyllithium, hexyllithium, n-decyllithium, t-octyllithium, phenyllithium, 1-naphthyllithium, n-eicosyllithium, 4-butylphenyllithium, 4-tolyl Lithium, cyclohexyl lithium, 3,5-di-n-heptylcyclohexyl lithium, 4-cyclopentyl lithium, naphthyl sodium, naphthyl potassium, lithium alkoxide, sodium alkoxide, potassium alkoxide, lithium sulfonate, sodium sulfonate, It may be at least one selected from the group consisting of potassium sulfonate, lithium amide, sodium amide, potassium amide and lithium isopropylamide.

According to an embodiment of the present invention, the polymerization initiator may be used in an amount of 0.01 mmol to 10 mmol, 0.05 mmol to 5 mmol, 0.1 mmol to 2 mmol, 0.1 mmol to 1 mmol, or 0.15 to 0.8 mmol per 100 g of the monomer. . Here, the monomer may represent the content of the conjugated diene-based monomer or the total amount of the conjugated diene-based monomer and the aromatic vinyl-based monomer.

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, and the elevated temperature polymerization may refer to a polymerization method in which the temperature is increased by arbitrarily 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, the polymerization of step (S1) may be performed through a batch reaction, a continuous reaction, or a reaction combining them appropriately.

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, and in this case, it is applied to the reactor wall during long-term operation. It has the effect of preventing the formation of a gel. The diene-based compound may be, for example, 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 There is an effect of increasing the polymerization conversion rate of the polymerization reaction within.

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

In addition, 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 (2-dimethylaminoethyl) ether, (dimethylaminoethyl) ethyl ether, trimethylamine, triethylamine, tripropylamine, N,N,N',N'-tetramethyl It may be at least one 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 In the case of copolymerizing a monomer or a conjugated diene-based monomer and an aromatic vinyl-based monomer, there is an effect of inducing a random copolymer to be easily formed by compensating for a difference in their reaction rate.

According to an embodiment of the present invention, the reaction in step (S2) may be a denaturation reaction or a coupling reaction using a sulfamoylfluoride group-containing compound represented by Formula 1, in which case, the sulfamoylfluoride group-containing compound The compound may be used in an amount of 0.01 mmol to 10 mmol based on 100 g of the total monomer. As another example, the sulfamoylfluoride group-containing compound may be used in an amount of 0.1 mol to 10 mol, 0.1 mol to 5 mol, or 0.1 mol to 3 mol based on 1 mol of the polymerization initiator in step (S1).

rubber composition

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

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 thereof include wet silica (hydrous silicic acid), dry silica (silicic anhydride), calcium silicate, aluminum silicate or colloidal silica, and preferably, the effect of improving the breaking 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 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 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, ZnO), 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 abrasion resistance by a vulcanization process after molding processing. This excellent rubber composition can be obtained.

Accordingly, the rubber composition may include each member of the tire, such as a tire tread, under tread, sidewall, carcass coated rubber, belt coated rubber, bead filler, chaff, 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, examples will be given to describe the present invention 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.

In addition, the materials used in the following Examples and Comparative Examples were prepared and used with reference to conventionally known manufacturing methods, or purchased and used materials in circulation, except for those mentioned in particular.

Preparation Example 1

In a 2-neck round-bottom flask, 10 mmol of diallylamine, 10 mmol of 4-dimethylaminopyridine (DMAP) and 20 mmol of triethylamine were added, and 30 ml of dichloromethane (CH ₂ Cl ₂ ) was added and stirred. Then, SO ₂ F ₂ The filled balloon was connected to the 2-neck of the flask and stirred while flowing slowly at room temperature (about 25° C.) for 12 hours. Then, 100 ml of dichloromethane was added to dissolve the mixture in the flask, washed with 1N HCl, and water was removed with MgSO ₄ . Then, 6.5 mmol of the compound represented by the following Chemical Formula 1-1 was prepared by purification by vacuum distillation and silica gel column chromatography. ¹ H nuclear magnetic resonance spectroscopy was observed to confirm that the compound was prepared.

[Formula 1-1]

¹ H NMR (500 MHz, CDCl ₃ ): δ = 5.81 (ddtd, J=16.8, 10.2, 6.5, 1.1 Hz, 2H), 5.36-5.28 (m, 4H), 3.94 (d, J=6.3 Hz, 4H) ).

Preparation 2

It was carried out in the same manner as in Preparation Example 1, except that 10 mmol of 2.5-dihydro-1H-pyrrole (2,5-dihydro-1H-pyrrole) was used instead of diallylamine in Preparation Example 1, and represented by Formula 1-2 7.1 mmol of the compound used were prepared. ¹ H nuclear magnetic resonance spectroscopy was observed to confirm that the compound was prepared.

[Formula 1-2]

¹ H NMR (500 MHz, CDCl ₃ ): δ = 5.80-5.70 (m, 2H), 3.28-3.16 (m, 4H).

Preparation 3

8.1 mmol of a compound represented by Formula 1-3 was prepared in the same manner as in Preparation Example 1, except that 10 mmol of aniline was used instead of diallylamine in Preparation Example 1. ¹ H nuclear magnetic resonance spectroscopy was observed to confirm that the compound was prepared.

[Formula 1-3]

¹ H NMR (400 MHz, CD ₃ CN): δ = 7.72-7.62 (m).

Preparation 4

8.1 mmol of a compound represented by Formula 1-4 was prepared in the same manner as in Preparation Example 1, except that 10 mmol of piperazine was used instead of diallylamine in Preparation Example 1. ¹ H nuclear magnetic resonance spectroscopy was observed to confirm that the compound was prepared.

[Formula 1-4]

¹ H NMR (400 MHz, (CD ₃ ) ₂ CO): δ = 3.76 (s).

Preparation 5

In a 2-neck round-bottom flask, 10 mmol of piperazine and 11 mmol of triethylamine were added, and 20 ml of dichloromethane (CH ₂ Cl ₂ ) was added and stirred. The temperature was adjusted to 78°C, and 10 ml of a dichloromethane solution in which 10 mmol of SO ₂ Cl ₂ was dissolved was slowly added dropwise while controlling the temperature to be maintained at 0°C. After the addition was completed, stirring was continued for 2 hours while maintaining 0 °C. After adding 40 ml of cold water, the organic layer was washed with 1N HCl and water, and moisture was removed with MgSO ₄ . This was subjected to dark distillation to prepare 1-piperazinesulfonyl chloride.

In a 2-neck round-bottom flask, 10 mmol of the prepared 1-piperazinesulfonyl chloride, 10 mmol of 4-dimethylaminopyridine (DMAP) and 20 mmol of triethylamine were placed, and 30 ml of dichloromethane (CH ₂ Cl ₂ ) was added and stirred. Then, SO ₂ F ₂ The filled balloon was connected to the 2-neck of the flask and stirred while flowing slowly at room temperature (about 25° C.) for 12 hours. Then, 100 ml of dichloromethane was added to dissolve the mixture in the flask, washed with 1N HCl, and water was removed with MgSO ₄ . Then, 6.5 mmol of the compound represented by the following Chemical Formula 1-1 was prepared by purification by vacuum distillation and silica gel column chromatography. ¹ H nuclear magnetic resonance spectroscopy was observed to confirm that the compound was prepared.

[Formula 1-5]

¹ H NMR (500 MHz, CDCl ₃ ): δ = 2.95 (m, 4H).

Example 1

After putting 270 g of styrene, 710 g of 1,3-butadiene, 5000 g of n-hexane and 0.70 g of 2,2-di(2-tetrahydrofuryl)propane as a polar additive in a 20 L autoclave reactor, the internal temperature of the reactor was increased to 50 The temperature was raised to °C. When the internal temperature of the reactor reached 50° C., 3.0 mmol of n-butyllithium was added as a polymerization initiator to conduct an adiabatic temperature rise reaction. After about 60 minutes, 20 g of 1,3-butadiene was added, and the end of the polymer chain was capped with butadiene. After 5 minutes, the compound represented by Formula 1-1 prepared in Preparation Example 1 was added as a modifier and reacted for 30 minutes ([act. Li]:[Formula 1-1]=1:1 molar ratio). Then, the polymerization reaction was stopped using ethanol, and 45 ml of a solution in which an antioxidant IR1520 (BASF) was dissolved in n-hexane at 0.3 wt% was added. The resulting polymer was put into hot water heated with steam and stirred to remove the solvent to prepare a modified conjugated diene-based polymer.

Example 2

In Example 1, the compound represented by Formula 1-2 prepared in Preparation Example 2 was added instead of the compound represented by Formula 1-1 prepared in Preparation Example 1, and the denaturation reaction was performed. A modified conjugated diene-based polymer was prepared through the same method as in 1 ([act. Li]:[Formula 1-2]=1:1 molar ratio).

Example 3

In Example 1, the compound represented by Formula 1-3 prepared in Preparation Example 3 was added instead of the compound represented by Formula 1-1 prepared in Preparation Example 1, and the denaturation reaction was performed. A modified conjugated diene-based polymer was prepared through the same method as in 1 ([act. Li]:[Formula 1-3]=1:1 molar ratio).

Example 4

In Example 1, the compound represented by Formula 1-4 prepared in Preparation Example 4 was added instead of the compound represented by Formula 1-1 prepared in Preparation Example 1, and the denaturation reaction was performed. A modified conjugated diene-based polymer was prepared through the same method as in 1 ([act. Li]:[Formula 1-4]=1:1 molar ratio).

Example 5

In Example 1, the compound represented by Formula 1-5 prepared in Preparation Example 5 was added instead of the compound represented by Formula 1-1 prepared in Preparation Example 1, and the denaturation reaction was performed. A modified conjugated diene-based polymer was prepared through the same method as in 1 ([act. Li]:[Formula 1-5]=1:1 molar ratio).

Comparative Example 1

After putting 270 g of styrene, 730 g of 1,3-butadiene, 5000 g of n-hexane and 0.70 g of 2,2-di(2-tetrahydrofuryl)propane as a polar additive in a 20 L autoclave reactor, the internal temperature of the reactor was increased to 50 The temperature was raised to °C. When the internal temperature of the reactor reached 50° C., 2.1 mmol of n-butyllithium was added as a polymerization initiator to conduct adiabatic temperature increase for 60 minutes. Then, the polymerization reaction was stopped using ethanol, and 45 ml of a solution in which an antioxidant IR1520 (BASF) was dissolved in n-hexane at 0.3 wt% was added. The resulting polymer was put into hot water heated with steam and stirred to remove the solvent to prepare an unmodified conjugated diene-based polymer.

Comparative Example 2

In Example 1, N-methyl-3-(triethoxysilyl)-N-(3-(triethoxysilyl)propyl)propane instead of the compound represented by Formula 1-1 prepared in Preparation Example 1 as a modifier The same method as in Example 1, except that -1-amine (N-methyl-3-(triethoxysilyl)-N-(3-(triethoxysilyl)propyl)propan-1-amine) was added to carry out the denaturation reaction A modified conjugated diene-based polymer was prepared through ([act. Li]:[modifier]=1:1 molar ratio).

Experimental Example 1

For each modified or unmodified conjugated diene-based polymer prepared in Examples and Comparative Examples, styrene unit content and vinyl content, weight average molecular weight (Mw, X10 ³ g/mol), molecular weight distribution (PDI, MWD) in the polymer, respectively , Mooney viscosity and Mooney stress relaxation rate were measured, respectively. 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. A sample was prepared by dissolving 10 mg of a polymer in 1 ml of 1,1,2,2-tetrachloroethane.

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

GPC (Gel permeation Chromatography) (PL GPC220, Agilent Technologies) was used to measure the weight average molecular weight (Mw) and number average molecular weight (Mn) under the following conditions, and the molecular weight distribution (PDI, MWD, Mw / Mn) was measured Calculated from each molecular weight.

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

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

- Flow rate: 1 ml/min

- Sample concentration: 1~2 mg/ml (at 40℃, diluted in THF for 30 minutes)

- Injection volume: 100 μl

- Column temperature: 40℃

- Detector: Refractive index

- Reference material: Polystyrene (corrected by cubic function)

3) Mooney viscosity and Mooney stress relaxation rate (-S/R)

Using a Large Rotor of Alpha Technologies MV2000, at 100°C and a rotor speed of 2±0.02 rpm, the polymer was left at room temperature (23±3°C) for more than 30 minutes, and then 27±3 g was collected and placed inside the die cavity. After filling, the Mooney viscosity was measured while applying a torque by operating a platen. In addition, the slope value of the change in Mooney viscosity appearing as the torque is released was measured, and the absolute value thereof was used as the Mooney stress relaxation ratio.

division Example comparative example One 2 3 4 5 One 2 NMR
(weight%) SM 27.5 27.4 27.5 27.1 27.3 26.9 27.4 Vinyl 45.4 45.1 45.6 45.3 45.4 44.8 45.7 GPC Mw (X10 ³ g/mol) 91.6 90.5 89.7 90.8 89.1 86.2 107.1 PDI 2.19 2.00 1.86 1.95 1.83 1.62 2.02 Mooney viscosity 92 89 90 90 91 84 88 Mooney stress relaxation rate 0.616 0.652 0.689 0.671 0.669 0.710 0.638

As shown in Table 1, it was confirmed that the modified conjugated diene-based polymers of Examples 1 to 5 increased the weight average molecular weight and decreased the Mooney stress relaxation rate compared to the unmodified conjugated diene-based polymer of Comparative Example 1.

In general, the higher the degree of branching in a polymer, the lower the Mooney stress relaxation rate tends to be.

From these results, it can be confirmed that the branching of the modified conjugated diene-based polymers of Examples 1 to 5 is increased, and through this, the modified conjugated diene-based polymer according to the present invention is a sulfamoylfluoride group-containing compound represented by Formula 1 It can be confirmed that it has been transformed into

Experimental Example 2

In order to comparatively analyze the physical properties of the rubber composition containing each modified or unmodified conjugated diene-based copolymer prepared in Examples and Comparative Examples and molded articles prepared therefrom, tensile properties and viscoelastic properties were measured respectively and the results were obtained. It is shown in Table 3 below.

1) Preparation of rubber specimens

Each modified or unmodified conjugated diene-based polymer of Examples and Comparative Examples was compounded under the compounding conditions shown in Table 2 below as raw rubber. 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 25 Zincizing agent 3 stearic acid 2 antioxidant 2 anti-aging agent 2 wax One rubber accelerator 1.75 2nd stage kneading sulfur 1.5 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 oxide (ZnO), stearic acid is used using a Banbari mixer with a temperature control device. , antioxidant (TMQ(RD) (2,2,4-trimethyl-1,2-dihydroquinoline polymer), antioxidant (6PPD ((dimethylbutyl)-N-phenyl-phenylenediamine), wax (Microcrystaline Wax) ) and a rubber accelerator (DPG (diphenylguanidine)) were kneaded. At this time, the initial temperature of the kneader was controlled to 70° C., and after the mixing was completed, the first mixture was obtained at a discharge temperature of 150° C. In the second stage kneading After cooling the first blend to room temperature, the first blend, sulfur and a vulcanization accelerator (CZ (N-cyclohexyl-2-benzothiazylsulfenamide)) were added to a kneader, and mixed at a temperature of 100° C. or less to 2 A tea blend was obtained, and then, a rubber specimen was prepared through a curing process at 150° C. for 20 minutes.

2) Wear resistance (DIN wear test)

For each rubber specimen, a DIN abrasion test was performed according to ASTM D5963, and it was shown as DIN loss index (loss volume index): ARIA (Abration resistance index, Method A). In Table 3, the results are compared It is shown as an index based on Example 1, and the higher the number, the better.

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℃ tan value, the better the wet road resistance. Since the result value is expressed as an index based on Comparative Example 1, the higher the numerical value, the better.

division Example comparative example One 2 3 4 5 One 2 wear resistance 105 106 105 107 104 100 103 Viscoelastic properties
(Index, %) tan δ
(at 0°C) 101 100 102 101 100 100 102 tan δ
(at 60℃) 107 106 109 113 109 100 103

As shown in Table 3, it was confirmed that Examples 1 to 5 were generally excellent in abrasion resistance and viscoelastic properties compared to Comparative Examples 1 and 2.

In particular, Examples 1 to 5 exhibited an equivalent level of wet road resistance (0°C tan δ) compared to Comparative Example 2, while improving abrasion resistance and significantly improved by 3% to 10% in rolling resistance characteristics (60°C tan δ) effect was shown.

Through this, the modified conjugated diene-based polymer modified with a sulfamoylfluoride group-containing compound represented by Formula 1 according to the present invention and containing a functional group derived from the compound has better wear resistance and viscoelastic properties than the modified conjugated diene-based polymer modified with other modifiers. It can be seen that there is an excellent effect.

Claims (14)

a repeating unit derived from a conjugated diene-based monomer; and
A modified conjugated diene-based polymer comprising a functional group derived from a sulfamoylfluoride group-containing compound represented by the following formula (1):
[Formula 1]

In Formula 1,
R ₁ , R ₂ and R ₄ are each independently an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or —SO ₂ A (here In , A is F or Cl), R ₁ and R ₂ are connected to each other to form a saturated or unsaturated heterocyclic group having 3 to 10 carbon atoms together with N, or R ₂ and R ₄ are connected to each other to form N and together with R ₃ to form a C 3 to C 10 heterocyclic group,
R ₃ is an alkylene group having 1 to 10 carbon atoms,
a is 0 or 1.
According to claim 1,
In Formula 1,
a is 0,
R ₁ and R ₂ are each independently an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, or —SO ₂ A (here, A is F or Cl), or R ₁ and R ₂ are linked to each other to form an unsaturated heterocyclic group having 3 to 6 carbon atoms together with N. A modified conjugated diene-based polymer.
According to claim 1,
In Formula 1,
a is 1,
R ₁ is —SO ₂ A (wherein A is F or Cl),
R ₂ and R ₄ are linked to each other to form a C 3 to C 6 heterocyclic group together with N and R ₃ A modified conjugated diene-based polymer.
According to claim 1,
The sulfamoylfluoride group-containing compound represented by Formula 1 is a modified conjugated diene-based polymer that is at least one selected from compounds represented by Formulas 1-1 to 1-5 below:
[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

.
According to claim 1,
A modified conjugated diene-based polymer further comprising a repeating unit derived from an aromatic vinyl-based monomer.
According to claim 1,
A modified conjugated diene-based polymer having a Mooney viscosity of 30 to 150 measured at 100°C.
According to claim 1,
A modified conjugated diene-based polymer having a weight average molecular weight of 300,000 g/mol to 3,000,000 g/mol, and a molecular weight distribution of 1.0 to 5.0.
preparing an active polymer by 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 (S1); and
A method for producing the modified conjugated diene-based polymer of claim 1, comprising the step (S2) of reacting or coupling the active polymer with a sulfamoylfluoride group-containing compound represented by the following formula (1):
[Formula 1]

In Formula 1,
R ₁ , R ₂ and R ₄ are each independently an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or —SO ₂ A (here In , A is F or Cl), R ₁ and R ₂ are connected to each other to form a saturated or unsaturated heterocyclic group having 3 to 10 carbon atoms together with N, or R ₂ and R ₄ are connected to each other to form N and together with R ₃ to form a C 3 to C 10 heterocyclic group,
R ₃ is an alkylene group having 1 to 10 carbon atoms,
a is 0 or 1.
9. The method of claim 8,
The sulfamoylfluoride group-containing compound represented by Formula 1 is at least one selected from compounds represented by Formulas 1-1 to 1-5.
[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

.
9. The method of claim 8,
The polymerization initiator is a method for producing a modified conjugated diene-based polymer is used in an amount of 0.01 to 10 mmol per 100 g of the monomer.
9. The method of claim 8,
The sulfamoylfluoride group-containing compound represented by Formula 1 is used in an amount of 0.1 mol to 10 mol based on 1 mol of the polymerization initiator.
9. The method of claim 8,
The polymerization of the step (S1) is a method for producing a modified conjugated diene-based polymer to be carried out by further using a polar additive.
A rubber composition comprising the modified conjugated diene-based polymer of claim 1 and a filler.
14. The method of claim 13,
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.