WO2018128291A1 - Modified conjugated diene polymer and rubber composition comprising same - Google Patents

Abstract

The present invention relates to a modified conjugated diene polymer, more specifically, the invention provides: a modified conjugated diene polymer in which the molecular weight-distribution curve obtained by means of gel permeation chromatography (GPC) has a unimodal form, the molecular weight distribution (PDI;MWD) is less than 1.7 and the Si content is 150 ppm or more based on weight; and a rubber composition comprising the same.

Description

Modified conjugated diene polymer and rubber composition comprising same

[Citations with Related Applications]

This application claims the benefit of priority based on Korean Patent Application No. 10-2017-0000750 filed on January 1, 2017 and Korean Patent Application No. 10-2017-0097190 filed on July 31, 2017, and all contents disclosed in the documents of the Korean patent application. Is included as part of this specification.

[Technical Field]

The present invention relates to a modified conjugated diene-based polymer, and more particularly, to a modified conjugated diene-based polymer prepared by continuous polymerization, having excellent processability, and having a narrow molecular weight distribution and excellent physical properties, and a rubber composition comprising the same.

Recently, in accordance with the demand for low fuel consumption for automobiles, there has been a demand for conjugated diene-based polymers having low rolling resistance, excellent wear resistance and tensile characteristics, and adjustment stability represented by wet road resistance 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. As an evaluation index of the vulcanized rubber, a repulsive elasticity of 50 ° C. to 80 ° C., tan δ, Goodrich heat generation and the like are used. That is, a rubber material having a high resilience at the above temperature, or a small tan δ and good rich 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 wet road resistance. Recently, conjugated diene-based polymers or copolymers such as styrene-butadiene rubber (hereinafter referred to as SBR) or butadiene rubber (hereinafter referred to as BR) have been produced by emulsion polymerization or solution polymerization and used as rubber for tires. . Among them, the greatest advantage of solution polymerization over emulsion polymerization is that the vinyl structure content and styrene content that define rubber properties can be arbitrarily controlled, and molecular weight and physical properties can be controlled by coupling or modification. Can be. Therefore, it is easy to change the structure of the final manufactured SBR or BR, and can reduce the movement of the chain end by the binding or modification of the chain end and increase the bonding strength with the filler such as silica or carbon black. It is widely used as a rubber material.

When such a solution polymerization SBR is used as a rubber material for tires, by increasing the vinyl content in the SBR, the glass transition temperature of the rubber can be increased to not only control tire demand properties such as running resistance and braking force, but also increase the glass transition temperature. Proper adjustment can reduce fuel consumption. The solution polymerization SBR is prepared using an anionic polymerization initiator, and is used by binding or modifying the chain ends of the formed polymer using various modifiers. For example, US Pat. No. 4,397,994 discloses a technique in which the active anion at the chain end of a polymer obtained by polymerizing styrene-butadiene in a nonpolar solvent using alkyllithium, which is a monofunctional initiator, is bound using a binder such as a tin compound. It was.

On the other hand, the polymerization of the SBR or BR may be carried out by batch (batch) or continuous polymerization, by the batch polymerization, the molecular weight distribution of the polymer produced is advantageous in terms of improving the physical properties, but the productivity is low and There is a problem of poor workability, and in case of the continuous polymerization, the polymerization is continuously made, thus the productivity is excellent, and there is an advantage in terms of processability improvement. However, there is a problem of poor physical properties due to wide molecular weight distribution. Thus, in the production of SBR or BR, the situation is constantly being researched to improve both productivity, processability and physical properties at the same time.

The present invention has been made in order to solve the problems of the prior art, a modified conjugated diene-based polymer prepared by continuous polymerization and excellent in processability, excellent physical properties such as tensile properties, excellent viscoelastic properties, and the like It is an object to provide a rubber composition.

According to an embodiment of the present invention for solving the above problems, the present invention has a molecular weight distribution curve by gel permeation chromatography (GPC) has a unimodal form, molecular weight distribution (PDI; MWD) is less than 1.7 to provide a modified conjugated diene-based polymer having a Si content of 100 ppm or more by weight.

The present invention also provides a rubber composition comprising the modified conjugated diene-based polymer and a filler.

Since the modified conjugated diene-based polymer according to the present invention is produced for continuous polymerization, it has excellent processability and has a narrow molecular weight distribution that is equivalent to or higher than that of the modified conjugated diene-based polymer produced by batch polymerization. It is excellent in physical properties and excellent in viscoelastic properties.

The following drawings, which are attached to this specification, illustrate exemplary embodiments of the present invention, and together with the contents of the present invention serve to further understand the technical idea of the present invention, the present invention is limited to the matters described in such drawings. It should not be construed as limited.

Figure 1 shows the molecular weight distribution curve by gel permeation chromatography (GPC) of the modified conjugated diene-based polymer of Example 3 according to an embodiment of the present invention.

Figure 2 shows the molecular weight distribution curve by gel permeation chromatography (GPC) of the modified conjugated diene-based polymer of Example 6 according to an embodiment of the present invention.

Figure 3 shows the molecular weight distribution curve by gel permeation chromatography (GPC) of the modified conjugated diene-based polymer of Comparative Example 3 according to an embodiment of the present invention.

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

The terms or words used in the description and claims of the present invention should not be construed as being limited to the ordinary or dictionary meanings, and the inventors should properly explain the concept of terms in order to explain their invention in the best way. Based on the principle that it can be defined, it should be interpreted as meaning and concept corresponding to the technical idea of the present invention.

The modified conjugated diene-based polymer according to the present invention has a molecular weight distribution curve by gel permeation chromatography (GPC) has a unimodal form, a molecular weight distribution (PDI; MWD) is less than 1.7, Si content It may be at least 100 ppm based on this weight.

According to one embodiment of the present invention, the modified conjugated diene-based polymer may include a repeating unit derived from a conjugated diene monomer and a functional group derived from a modifier. The conjugated diene-based monomer-derived repeating unit may mean a repeating unit formed when the conjugated diene-based monomer is polymerized, and the modifier-derived functional group is present at one end of the active polymer through a reaction or coupling between the active polymer and the modifying agent. It can mean a functional group derived from.

In this case, the modified conjugated diene-based polymer may be a homopolymer including a conjugated diene-based monomer-derived repeating unit that does not include an aromatic vinyl monomer-derived repeating unit.

According to one embodiment of the invention, the conjugated diene 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 halogen atom).

On the other hand, the modified conjugated diene-based polymer may be a copolymer comprising a conjugated diene-based repeating unit and an aromatic vinyl monomer-derived repeating unit, in which case the modified conjugated diene-based polymer is a repeating unit derived from an aromatic vinyl monomer More than 0 wt% and less than 10 wt%.

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 ) 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 diene-based monomer derived from C 1 to 10 together with the repeating unit derived from the conjugated diene monomer. The diene monomer-derived repeating unit may be a repeating unit derived from a diene monomer different from the conjugated diene monomer, and the diene monomer different from the conjugated diene monomer may be, for example, 1,2-butadiene. . When the modified conjugated diene-based polymer is a copolymer further comprising a diene monomer, the modified conjugated diene-based polymer is more than 0% to 1% by weight, greater than 0% to 0.1% by weight of the repeating unit derived from the diene monomer, It may be included in more than 0% by weight to 0.01% by weight, or more than 0% by weight to 0.001% by weight, there is an effect of preventing the gel production within this range.

According to one embodiment of the invention, the copolymer may be a random copolymer, in this case there is an excellent balance between the physical properties. The random copolymer may mean that the repeating units constituting the copolymer are 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, the weight average molecular weight (Mw) may be 1,000 g / mol to 3,000,000 g / mol, 10,000 g / mol to 2,000,000 g / mol, or 100,000 g / mol to 2,000,000 g / mol, within this range Cloud resistance and wet road resistance is excellent effect. As another example, the modified conjugated diene-based polymer may have a molecular weight distribution (PDI; MWD; Mw / Mn) of less than 1.7, 1.0 or more and less than 1.7, or 1.1 or more and less than 1.7, and tensile and viscoelastic properties within this range. It is excellent in this and there exists an effect which is excellent in the balance between each physical property. At the same time, the modified conjugated diene-based polymer has a molecular weight distribution curve by gel permeation chromatography (GPC) has a unimodal form, which is a molecular weight distribution appearing in the polymer polymerized by continuous polymerization As such, it may mean that the modified conjugated diene-based polymer has a uniform characteristic. That is, the modified conjugated diene-based polymer according to an embodiment of the present invention may be prepared by continuous polymerization, and may have a molecular weight distribution curve of less than 1.7 while having a unimodal molecular weight distribution curve.

As another example, the modified conjugated diene-based polymer may have a Si content of 100 ppm or more, 100 ppm to 10,000 ppm, or 100 ppm to 5,000 ppm by weight, and includes a modified conjugated diene-based polymer within this range. There is an effect excellent in mechanical properties such as tensile properties and viscoelastic properties of the rubber composition. The Si content may refer to the content of Si atoms present in the modified conjugated diene-based polymer. Meanwhile, the Si atom may be derived from a modifier-derived functional group.

For example, the Si content may be measured by an ICP analysis method, and the ICP analysis method may be measured by an acid decomposition pretreatment method using an inductively coupled plasma luminescence analyzer (ICP-OES; Optima 7300DV). In the case of using the inductively coupled plasma luminescence analyzer, about 0.7 g of the sample was placed in a platinum crucible (Pt crucible), about 1 mL of concentrated sulfuric acid (98 wt%, Electronic grade) was heated at 300 ° C. for 3 hours, and the sample was After the conversation in the electric furnace (Thermo Scientific, Lindberg Blue M) in the program of steps 1 to 3,

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

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

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

1 mL of concentrated nitric acid (48% by weight) and 20 μl of concentrated hydrofluoric acid (50% by weight) were added, the crucible was sealed and shaken for at least 30 minutes, and then 1 mL of boric acid was added to the sample. After storage for 2 hours or more at 0 ℃, diluted in 30 mL of ultrapure water (ultrapure water), it may be measured by proceeding incineration.

As another example, the modified conjugated diene-based polymer has a polymer component of at least 100,000 g / mol of molecular weight in terms of standard polystyrene converted by gel permeation chromatography, unimodal, a molecular weight distribution (PDI; MWD) of 2.0 or less, and a number average molecular weight. Content of a polymer component having a (Mn) of 250,000 g / mol to 700,000 g / mol, a vinyl content of butadiene units of 20 mol% to 80 mol% or less, a Si content of 100 ppm or more based on weight, and having a functional group 50 wt% or more, and may include more than 0 wt% to less than 15 wt% of the aromatic vinyl monomer-derived repeating unit.

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 excellent workability and productivity within this range.

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

The modifier according to the present invention may be a modifier for modifying the terminal of the conjugated diene-based polymer, may be an alkoxy silane-based modifier, and more specifically an alkoxy silane-based modifier containing a nitrogen atom. In the case of using the alkoxy silane-based modifier, modification may be performed in a form in which one end of the active polymer is bonded to the silyl group through a substitution reaction between an anion active site located at one end of the active polymer and an alkoxy group of the alkoxy silane-based modifier. Thereby, affinity with the inorganic filler and the like is improved from the modifier-derived functional group present at one end of the modified conjugated diene-based polymer, thereby improving mechanical properties of the rubber composition including the modified conjugated diene-based polymer. In addition, in the case where the alkoxy silane-based modifier contains a nitrogen atom, in addition to the effect derived from the silyl group, additional physical properties derived from the nitrogen atom can be expected.

According to one embodiment of the present invention, the denaturant may be to include a compound represented by the following formula (1).

[Formula 1]

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

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

In Formula 1, when R ⁴ is a heterocyclic group, the heterocyclic group may be unsubstituted or substituted with a trisubstituted alkoxy silyl group, when the heterocyclic group is substituted with a trisubstituted alkoxy silyl group, the trisubstituted alkoxy silyl group The heterocyclic group may be substituted by an alkylene group having 1 to 10 carbon atoms, and the trisubstituted alkoxy silyl group may mean an alkoxy silyl group substituted with an alkoxy group having 1 to 10 carbon atoms. The compound represented by 1 is N, N-bis (3- (dimethoxy (methyl) silyl) propyl) -methyl-1-amine (N, N-bis (3- (dimethoxy (methyl) silyl) propyl) -methyl -1-amine), N, N-bis (3- (diethoxy (methyl) silyl) propyl) -methyl-1-amine (N, N-bis (3- (diethoxy (methyl) silyl) propyl) -methyl -1-amine), N, N-bis (3- (trimethoxysilyl) propyl) -methyl-1-amine (N, N-bis (3- (trimethoxysilyl) propyl) -methyl-1-amine), N, N-bis (3- (triethoxysilyl) propyl) -methyl-1-amine (N, N-bis (3- (triethoxysilyl) propyl) -methyl-1-amine), N, N-diethyl-3- (tri Methoxysilyl) propan-1-amine (N, N-diethyl-3- (trimethoxysilyl) propan-1-amine), N, N-diethyl-3- (triethoxysilyl) propan-1-amine (N , N-diethyl-3- (triethoxysilyl) propan-1-amine), tri (trimethoxysilyl) amine, tri (3- (trimethoxysilyl) propyl) amine (tri- ( 3- (trimethoxysilyl) propyl) amine), N, N-bis (3- (diethoxy (methyl) silyl) propyl) -1,1,1-trimethylsilaneamine (N, N-bis (3- (diethoxy ( methyl) silyl) propyl) -1,1,1-trimethlysilanamine), N, N-bis (3- (1H-imidazol-1-yl) propyl)-(triethoxysilyl) methane-1-amine (N , N-bis (3- (1H-imidazol-1-yl) propyl)-(triethoxysilyl) methan-1-amine), N- (3- (1H-1,2,4-triazol-1-yl) Propyl) -3- (trimethoxysilyl) -N- (3- (trimethoxysilyl) propyl) propan-1-amine (N- (3- (1H-1,2,4-triazole-1-yl ) propyl) -3- (trimethoxysilyl) -N- (trimethoxysilyl) propyl) propan-1-amine) , 3- (trimethoxysilyl) -N- (3-trimethoxysilyl) propyl) -N- (3- (1- (3- (trimethoxysilyl) propyl) -1H-1,2,4 -Triazol-3-yl) propyl) propan-1-amine (3- (trimethoxysilyl) -N- (3- (trimethoxysilyl) propyl) -N- (3- (1- (3- (trimehtoxysilyl) propyl)- 1H-1,2,4-triazol-3-yl) propyl) propan-1-amine), N, N-bis (2- (2-methoxyethoxy) ethyl) -3- (triethoxysilyl) Propane-1-amine (N, N-bis (2- (2-methoxyethoxy) ethyl) -3- (triethoxysilyl) propna-1-amine), N, N-bis (3- (triethoxysilyl) propyl) -2,5,8,11,14-pentaxahexadecane-16-amine (N, N-bis (3- (triethoxysilyl) propyl) -2,5,8,11,14-pentaoxahexadecan-16-amine) , N- (2,5,8,11,14-pentaxahexadecane-16-yl) -N- (3- (triethoxysilyl) propyl) -2,5,8,11,14-pentaoxa Hexadecane-16-amine (N- (2,5,8,11,14-pentaoxahexadecan-16-yl) -N- (3- (triethoxysilyl) propyl) -2,5,8,11,14-pentaoxahexadecan- 16-amine) and N- (3,6,9,12-tetraoxahexadecyl) -N- (3- (triethoxysilyl) propyl) -3,6,9,12-tetraoxahexadecane-1 Amines (N- (3,6,9,12-tetraoxahexadecyl) -N- (3- (triethoxysilyl) propyl) -3,6,9,12-tetraoxahexadecan-1-amine).

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

[Formula 2]

In Formula 2, R ⁵ , R ⁶ and R ⁹ may be each independently an alkylene group having 1 to 10 carbon atoms, and R ⁷ , R ⁸ , R ¹⁰ and R ¹¹ are each independently an alkyl group having 1 to 10 carbon atoms. R ¹² may be hydrogen or an alkyl group having 1 to 10 carbon atoms, b and c may each independently be 0, 1, 2 or 3, and b + c ≧ 1, and A may be

or

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

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

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

[Formula 3]

In Formula 3, A ¹ and A ² may each independently be a divalent hydrocarbon group having 1 to 20 carbon atoms, including or without an oxygen atom, and R ¹⁷ to R ²⁰ are each independently monovalent having 1 to 20 carbon atoms. It may be a hydrocarbon group, L ¹ to L ⁴ are each independently a divalent, trivalent or tetravalent alkylsilyl group substituted with an alkyl group having 1 to 10 carbon atoms, or a monovalent hydrocarbon group having 1 to 20 carbon atoms, or L ¹ and L ² and L ³ and L ⁴ may be linked to each other to form a ring having 1 to 5 carbon atoms, and when L ¹ and L ² and L ³ and L ⁴ are connected to each other to form a ring, the ring formed may be It may include one to three heteroatoms selected from the group consisting of N, O and S.

As a specific example, in Formula 3, A ¹ and A ² may be each independently an alkylene group of 1 to 10, R ¹⁷ to R ²⁰ may be each independently an alkyl group having 1 to 10 carbon atoms, L ¹ to L ⁴ is independently a tetravalent alkylsilyl group substituted with an alkyl group having 1 to 5 carbon atoms, an alkyl group having 1 to 10 carbon atoms, or L ¹ and L ² and L ³ and L ⁴ are connected to each other to form a ring having 1 to 3 carbon atoms When L ¹ and L ² and L ³ and L ⁴ are linked to each other to form a ring, the ring formed may include one or more heteroatoms selected from the group consisting of N, O, and S; It can contain three.

As a more specific example, the compound represented by Formula 3 is 3,3 '-(1,1,3,3-tetramethoxydisiloxane-1,3-diyl) bis (N, N-dimethylpropan-1-amine) (3,3 '-(1,1,3,3-tetramethoxydisiloxane-1,3-diyl) bis (N, N-dimethylpropan-1-amine), 3,3'-(1,1,3,3- Tetraethoxydisiloxane-1,3-diyl) bis (N, N-dimethylpropan-1-amine) (3,3 '-(1,1,3,3-tetraethoxydisiloxane-1,3-diyl) bis ( N, N-dimethylpropan-1-amine), 3,3 '-(1,1,3,3-tetrapropoxydisiloxane-1,3-diyl) bis (N, N-dimethylpropan-1-amine) (3,3 '-(1,1,3,3-tetrapropoxydisiloxane-1,3-diyl) bis (N, N-dimethylpropan-1-amine), 3,3'-(1,1,3,3- Tetramethoxydisiloxane-1,3-diyl) bis (N, N-diethylpropan-1-amine) (3,3 '-(1,1,3,3-tetramethoxydisiloxane-1,3-diyl) bis ( N, N-diethylpropan-1-amine), 3,3 '-(1,1,3,3-tetramethoxydisiloxane-1,3-diyl) bis (N, N-dipropylpropan-1-amine) (3,3 '-(1,1,3,3-tetramethoxydisiloxane-1,3-diyl) bis (N, N-dimpropylpropan-1-amine), 3,3'-(1,1,3,3- Tetraethoxydisiloxane Acid-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-tetra Toxydisiloxane-1,3-diyl) bis (N, N-dipropylpropan-1-amine) (3,3 '-(1,1,3,3-tetraethoxydisiloxane-1,3-diyl) bis (N , N-dipropylpropan-1-amine), 3,3 '-(1,1,3,3-tetrapropoxydisiloxane-1,3-diyl) bis (N, N-dipropylpropan-1-amine) (3,3 '-(1,1,3,3-tetrapropoxydisiloxane-1,3-diyl) bis (N, N-dipropylpropan-1-amine), 3,3'-(1,1,3,3- Tetramethoxydisiloxane-1,3-diyl) bis (N, N-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-tetraethoxydisiloxane-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-diethylmethane-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-tetrapropoxydisiloxane-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-amine) (3,3 '-(1,1,3,3-tetraethoxy disiloxane-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) Silaneamine (N, N '-((1,1,3,3-tetramethoxydisiloxane-1,3-diyl) bis (propan-3,1-diyl)) bis (1,1,1-trimethyl-N- ( trimethylsilyl) silanamine), N, N '-((1,1,3,3-tetraethoxydisiloxane-1,3-diyl) bis (propane-3,1-diyl)) bis (1,1,1 -Trimethyl-N- (trimethylsilyl) silaneamine (N, N '-((1,1,3,3-tetraethoxydisiloxane-1,3-diyl) bis (propan-3,1-diyl)) bis (1, 1,1-trimethyl-N- (trimethylsilyl) silanamine), N, N '-((1,1,3,3-tetrapropoxydisiloxane-1,3-diyl) bis (propane-3,1-diyl )) Bis (1,1,1-trimethyl-N- (trimethylsilyl) silaneamine (N, N '-((1,1,3,3-tetrapropoxydisiloxane-1,3-diyl) bis (propan-3, 1-diyl)) bis (1,1,1-trimethyl-N- (t rimethylsilyl) silanamine), N, N '-((1,1,3,3-tetramethoxydisiloxane-1,3-diyl) bis (propane-3,1-diyl)) bis (1,1,1- Trimethyl-N-phenylsilaneamine (N, N '-((1,1,3,3-tetramethoxydisiloxane-1,3-diyl) bis (propan-3,1-diyl)) bis (1,1,1- trimethyl-N-phenylsilanamine), N, N '-((1,1,3,3-tetraethoxydisiloxane-1,3-diyl) bis (propane-3,1-diyl)) bis (1,1 , 1-trimethyl-N-phenylsilaneamine (N, N '-((1,1,3,3-tetraethoxydisiloxane-1,3-diyl) bis (propan-3,1-diyl)) bis (1,1 , 1-trimethyl-N-phenylsilanamine), N, N '-((1,1,3,3-tetrapropoxydisiloxane-1,3-diyl) bis (propane-3,1-diyl)) bis ( 1,1,1-trimethyl-N-phenylsilaneamine (N, N '-((1,1,3,3-tetrapropoxydisiloxane-1,3-diyl) bis (propan-3,1-diyl)) bis ( 1,1,1-trimethyl-N-phenylsilanamine), 1,3-bis (3- (1H-imidazol-1-yl) propyl) 1,1,3,3-tetramethoxydisiloxane (1,3- bis (3- (1H-imidazol-1-yl) propyl) -1,1,3,3-tetramethoxydisiloxane), 1,3-bis (3- (1H-imidazol-1-yl) propyl) 1,1 , 3,3-tetraethoxydisiloxane (1,3-bi s (3- (1H-imidazol-1-yl) propyl) -1,1,3,3-tetraethoxydisiloxane), and 1,3-bis (3- (1H-imidazol-1-yl) propyl) 1, 1,3,3-tetrapropoxydisiloxane (1,3-bis (3- (1H-imidazol-1-yl) propyl) -1,1,3,3-tetrapropoxydisiloxane) may be one selected from the group consisting of have.

As another example, the denaturant may include a compound represented by the following Formula 4.

[Formula 4]

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

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

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

[Formula 4a]

[Formula 4b]

[Formula 4c]

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

As a specific example, the compound represented by Formula 4 is a more specific example, the compound represented by Formula 4 is 1,4-bis (3- (3- (triethoxysilyl) propoxy) propyl) piperazine (1 , 4-bis (3- (3- (triethoxysilyl) propoxy) propyl) piperazine, 1,4-bis (3- (triethoxysilyl) propyl) piperazine (1,4-bis (3- (triethoxysilyl) propyl ) piperazine), 1,4-bis (3- (trimethoxysilyl) propyl) piperazine (1,4-bis (3- (trimethoxysilyl) propyl) piperazine), 1,4-bis (3- (dimethoxy Methylsilyl) propyl) piperazine (1,4-bis (3- (dimethoxymethylsilyl) propyl) piperazine), 1- (3- (ethoxydimethylsilyl) propyl) -4- (3- (triethoxysilyl) propyl Piperazine (1- (3- (ethoxydimethlylsilyl) propyl) -4- (3- (triethoxysilyl) propyl) piperazine), 1- (3- (ethoxydimethyl) propyl) -4- (3- (triethoxy Silyl) methyl) piperazine (1- (3- (ethoxydimethyl) propyl) -4- (3- (triethoxysilyl) methyl) piperazine), 1- (3- (ethoxydimethyl) methyl) -4- (3- ( Triethoxysilyl) pro Piperazine (1- (3- (ethoxydimethyl) methyl) -4- (3- (triethoxysilyl) propyl) piperazine), 1,3-bis (3- (triethoxysilyl) propyl) imidazolidine (1 , 3-bis (3- (triethoxysilyl) propyl) imidazolidine), 1,3-bis (3- (dimethoxyethylsilyl) propyl) imidazolidine (1,3-bis (3- (dimethoxyethylsilyl) propyl) imidazolidine ), 1,3-bis (3- (trimethoxysilyl) propyl) hexahydropyrimidine (1,3-bis (3- (trimethoxysilyl) propyl) hexahydropyrimidine), 1,3-bis (3- (trie Methoxysilyl) propyl) hexahydropyrimidine (1,3-bis (3- (triethoxysilyl) propyl) hexahydropyrimidine) and 1,3-bis (3- (tributoxysilyl) propyl) -1,2,3,4 Tetrahydropyrimidine (1,3-bis (3- (tributoxysilyl) propyl) -1,2,3,4-tetrahydropyrimidine) may be one selected from the group consisting of.

As another example, the denaturant may include a compound represented by the following Formula 5.

[Formula 5]

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

As another example, the denaturant may include a compound represented by the following Formula 6.

[Formula 6]

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

In another embodiment, the denaturing agent is 3,4-bis (2-methoxydeoxy) -N- (4- (triethoxysilyl) butyl) aniline (3,4-bis (2-methoxyethoxy) -N- ( 4- (trimethylsilyl) butyl) aniline), N, N-diethyl-3- (7-methyl-3,6,8,11-tetraoxa-7-silatridecan-7-yl) propan-1-amine (N, N-diethyl-3- (7-methyl-3,6,8,11-tetraoxa-7-silatridecan-7-yl) propan-1-amine), 2,4-bis (2-methoxyde Methoxy) -6-((trimethylsilyl) methyl) -1,3,5-triazine (2,4-bis (2-methoxyethoxy) -6-((trimethylsilyl) methyl) -1,3,5-triazine) And 3,14-dimethoxy-3,8,8,13-tetramethyl-2,14-dioxa-7,9-dithia-3,8,13-trasilapentadecane (3,13-dimethoxy- 3,8,8,13-tetramethyl-2,14-dioxa-7,9-dithia-3,8,13-trisilapentadecane) may be one or more selected from the group consisting of.

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

[Formula 7]

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

More specifically, the compound represented by Chemical Formula 7 is 8,8-dibutyl-3,13-dimethoxy-3,13-dimethyl-2,14-dioxa-7,9-dithia-3,13- Disila-8-stanpentadecane (8,8-dibutyl-3,13-dimethoxy-3,13-dimethyl-2,14-dioxa-7,9-dithia-3,13-disila-8-stannapentadecane), 8,8-dimethyl-3,13-dimethoxy-3,13-dimethyl-2,14-dioxa-7,9-dithia-3,13-disila-8-stanpentadecane (8,8- dimetyl-3,13-dimethoxy-3,13-dimethyl-2,14-dioxa-7,9-dithia-3,13-disila-8-stannapentadecane), 8,8-dibutyl-3,3,13, 13-tetramethoxy-2,14-dioxa-7,9-dithia-3,13-disila-8-stanpentadecane (8,8-dibutyl-3,3,13,13-tetramethoxy-2 , 14-dioxa-7,9-dithia-3,13-disila-8-stannapentadecane) and 8-butyl-3,3,13,13-tetramethoxy-8-((3- (trimethoxysilyl) Propyl) thio) -2,14-dioxa-7,9-dithia-3,13-disila-8-stanpentadecane (8-butyl-3,3,13,13-tetramethoxy-8-(( 3- (trimehtoxysilyl) propyl) thio) -2,14-dioxa-7,9-dithia-3,13-disila-8-stannapentadecane) from the group consisting of It may be one selected.

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

In the present invention, the term 'bivalent hydrocarbon group' is a two-membered carbon and hydrogen, such as a divalent alkylene group, an alkenylene group, an alkynylene group, a cycloalkylene group, a cycloalkylene group including one or more unsaturated bonds, and an arylene group. It may mean a valence atom group, and the minimum number of carbon atoms of a substituent represented by a divalent hydrocarbon may be determined according to the type of each substituent.

In the present invention, the term 'alkyl group' may mean a monovalent aliphatic saturated hydrocarbon, and may be linear alkyl groups such as methyl, ethyl, propyl and butyl, and isopropyl, sec-butyl, tertiary, It may be meant to include all branched alkyl groups such as tert-butyl and neo-pentyl.

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

In the present invention, the term 'alkenyl group' may refer to an alkyl group including one or two or more double bonds.

In the present invention, the term 'alkynyl group' may refer to an alkyl group including one or two or more triple bonds.

In the present invention, the term "cycloalkyl group" may mean both cyclic saturated hydrocarbons or cyclic unsaturated hydrocarbons containing one or two or more unsaturated bonds.

In the present invention, the term 'aryl group' may mean a cyclic 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 combined. hydrocarbons) can be included.

The present invention provides a method for producing a modified conjugated diene-based polymer in order to produce the modified conjugated diene-based polymer. The modified conjugated diene-based polymer manufacturing method comprises the steps of polymerizing or copolymerizing a conjugated diene-based monomer, or a conjugated diene-based monomer and an aromatic vinyl monomer in the presence of an organometallic compound in a hydrocarbon solvent to prepare an active metal combined with an organic metal. (S1); And reacting or coupling the active polymer prepared in the step (S1) with the denaturant (S2), wherein the step (S1) is carried out continuously in two or more polymerization reactors, and in the first reactor The polymerization conversion may be 50% or less.

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.

According to one embodiment of the invention, the organometallic compound 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 100 g of the total monomers Can be used as Examples of the organometallic compound include methyllithium, ethyllithium, propyllithium, isopropyllithium, n-butyllithium, s-butyllithium, t-butyllithium, hexyllithium, n-decyllithium, t-octylithium and phenyllithium. , 1-naphthyllithium, n-eicosilium, 4-butylphenyllithium, 4-tolyllithium, cyclohexyllithium, 3,5-di-n-heptylcyclohexyllithium, 4-cyclopentyllithium, naphthyl sodium And naphthyl potassium, lithium alkoxide, sodium alkoxide, potassium alkoxide, lithium sulfonate, sodium sulfonate, potassium sulfonate, lithium amide, sodium amide, potassium amide and lithium isopropylamide.

The polymerization of the step (S1) may be, for example, anionic polymerization, and specifically, may be living anion polymerization having an anion active site at the end of the polymerization by a growth polymerization reaction by anion. In addition, the polymerization of the step (S1) may be a temperature increase polymerization, isothermal polymerization or constant temperature polymerization (thermal insulation polymerization), the constant temperature polymerization may include the step of polymerization by the heat of reaction without the addition of heat after the addition of the organometallic compound optionally The temperature polymerization may mean a polymerization method in which the temperature is increased by optionally adding heat after the organometallic compound is added, and the isothermal polymerization is heat after adding the organometallic compound. By adding to increase the heat or take the heat may mean a polymerization method for maintaining a constant temperature of the polymer.

In addition, according to one embodiment of the present invention, the polymerization of the step (S1) may be carried out by further comprising a diene monomer having 1 to 10 carbon atoms in addition to the conjugated diene monomer, in this case, the reactor wall surface for a long time operation There is an effect of preventing the formation of a gel. The diene monomer may be 1,2-butadiene, for example.

The polymerization of the step (S1) may be carried out at 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. By narrowly adjusting the molecular weight distribution of the polymer within, there is an effect excellent in improving physical properties.

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

According to one embodiment of the present invention, the active polymer prepared by the polymerization of the step (S1) may be a random copolymer, in this case, the balance between the physical properties is excellent effect. The random copolymer may mean that the repeating units constituting the copolymer are randomly arranged.

According to one embodiment of the present invention, the modified conjugated diene-based polymer manufacturing method may be carried out by a continuous polymerization method in a plurality of reactors including two or more polymerization reactors and a modified reactor. As a specific example, the step (S1) may be carried out continuously in two or more polymerization reactors, and the number of the polymerization reactors may be elastically determined according to the reaction conditions and environment. The continuous polymerization method may mean a reaction process of continuously supplying a reactant to the reactor and continuously discharging the generated reaction product. In the case of the continuous polymerization method, it is excellent in productivity and processability and excellent in uniformity of the polymer to be produced.

Further, according to one embodiment of the present invention, when continuously producing the active polymer in the polymerization reactor, the polymerization conversion rate in the first reactor may be 50% or less, 10% to 50%, or 20% to 50%, After the polymerization reaction is initiated within this range, it is possible to suppress the side reactions generated when the polymer is formed to induce a polymer having a linear structure during the polymerization, thereby narrowing the molecular weight distribution of the polymer, The improvement is excellent.

In this case, the polymerization conversion may be adjusted according to the reaction temperature, the reactor residence time.

The polymerization conversion rate may be determined, for example, by measuring a solid concentration on a polymer solution containing a polymer when polymerizing the polymer. Specifically, in order to secure the polymer solution, a cylindrical container may be mounted at the outlet of each polymerization reactor. After filling the cylindrical solution with the positive polymer solution, and separating the cylindrical container from the reactor to measure the weight (A) of the cylinder filled with the polymer solution, the polymer solution filled in the cylindrical container was replaced with an aluminum container, As an example, the weight (B) of the cylindrical container which is transferred to an aluminum dish and the polymer solution is removed is measured, the aluminum container containing the polymer solution is dried in an oven at 140 ° C. for 30 minutes, and the weight (C) of the dried polymer is measured. After that, it may be calculated according to the following equation (1).

[Equation 1]

On the other hand, the polymerized in the first reactor is sequentially transferred to the polymerization reactor before the modification reactor, the polymerization may proceed until the polymerization conversion rate is at least 95%, and after the polymerization in the first reactor, the second reactor In addition, the polymerization conversion rate of each reactor from the second reactor to the polymerization reactor before the modified reactor may be carried out by appropriately adjusting the respective reactors to control the molecular weight distribution.

In the present invention, the term 'polymer' is carried out in each reactor during the step (S1), before the step (S1) or (S2) is completed to obtain an active polymer or a modified conjugated diene-based polymer. It can mean an intermediate in the form of a polymer being used, and can mean a polymer having a polymerization conversion of less than 99% in which polymerization is being carried out in the reactor.

According to one embodiment of the invention, the molecular weight distribution (PDI, polydispersed index; MWD, molecular weight distribution; Mw / Mn) of the active polymer prepared in step (S1) is less than 1.5, 1.0 or more to less than 1.5, or 1.1 The molecular weight distribution of the modified conjugated diene-based polymer prepared through the modification reaction or coupling with the modifier within this range may be less than or equal to 1.5, thereby improving the physical properties.

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

Examples of the polar additives include tetrahydrofuran, 2,2-di (2- (tetrahydrofuryl) propane, diethyl ether, cycloamal ether, dipropyl ether, ethylene methyl ether, ethylene dimethyl ether, diethyl glycol, and dimethyl. Ether, tert-butoxyethoxyethane, bis (3-dimethylaminoethyl) ether, (dimethylaminoethyl) ethyl ether, trimethylamine, triethylamine, tripropylamine, N, N, N ', N'-tetra It may be at least one selected from the group consisting of methyl ethylene diamine, sodium mentholate and 2-ethyl tetrahydrofurfuryl ether, preferably triethylamine, N, N, N ', N'-tetramethylethylenediamine, sodium mentholate or 2-ethyl tetrahydrofurfuryl ether, and when the polar additive is included conjugated diene-based When copolymerizing a monomer or a conjugated diene monomer and an aromatic vinyl monomer, it is possible to easily form a random copolymer by compensating for the difference in their reaction rates.

According to one embodiment of the present invention, the reaction or coupling of the step (S2) may be carried out in a modification reactor, wherein the denaturant may be used in an amount of 0.01 mmol to 10 mmol based on a total of 100 g of monomers. have. As another example, the denaturant 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 organometallic compound of step (S1).

In addition, according to an embodiment of the present invention, the denaturant may be added to the modification reactor, the step (S2) may be carried out in the modification reactor. As another example, the denaturant may be added to the transfer unit for transferring the active polymer prepared in the step (S1) to the modification reactor for performing the step (S2), and the mixture of the active polymer and the modifier in the transfer unit Reaction or coupling may proceed.

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

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

In addition, the rubber composition may further include other rubber components as needed in addition to the modified conjugated diene-based polymer, wherein the rubber components 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 part by weight to 900 parts by weight based on 100 parts by weight of the modified conjugated diene-based polymer.

The rubber component may be, for example, natural rubber or synthetic rubber, and specific examples include natural rubber (NR) including cis-1,4-polyisoprene; Modified natural rubbers such as epoxidized natural rubber (ENR), deproteinized natural rubber (DPNR), and hydrogenated natural rubber obtained by modifying or refining the general natural rubber; Styrene-butadiene copolymer (SBR), polybutadiene (BR), polyisoprene (IR), butyl rubber (IIR), ethylene-propylene copolymer, polyisobutylene-co-isoprene, neoprene, poly (ethylene-co- Propylene), poly (styrene-co-butadiene), poly (styrene-co-isoprene), poly (styrene-co-isoprene-co-butadiene), poly (isoprene-co-butadiene), poly (ethylene-co-propylene Co-diene), polysulfide rubber, acrylic rubber, urethane rubber, silicone rubber, epichlorohydrin rubber, butyl rubber, halogenated butyl rubber, etc., and any one or a mixture of two or more thereof may be used. have.

The rubber composition may include, for example, 0.1 part by weight to 200 parts by weight, or 10 parts by weight to 120 parts by weight of a filler based on 100 parts by weight of the modified conjugated diene polymer of the present invention. The filler may be, for example, a silica-based filler, and specific examples may be wet silica (silicate silicate), dry silica (silicate anhydrous), calcium silicate, aluminum silicate, colloidal silica, and the like. The wet silica may be the most compatible of the grip (wet grip). In addition, the rubber composition may further include a carbon black filler as needed.

As another example, when silica is used as the filler, a silane coupling agent for improving reinforcement and low heat generation may be used together. As a specific example, the silane coupling agent may include 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-dimethylthiocarbamoyl tetrasulfide, 3-triethoxysilylpropyl-N, N-dimethylthiocarbamoyl tetrasulfate Feed, 2-triethoxysilylethyl-N, N-dimethylthiocarbamoyl tetrasulfide, 3-trime Sisilylpropylbenzothiazolyl tetrasulfide, 3-triethoxysilylpropylbenzolyl tetrasulfide, 3-triethoxysilylpropyl methacrylate monosulfide, 3-trimethoxysilylpropyl methacrylate monosulfide , Bis (3-diethoxymethylsilylpropyl) tetrasulfide, 3-mercaptopropyldimethoxymethylsilane, dimethoxymethylsilylpropyl-N, N-dimethylthiocarbamoyltetrasulfide or dimethoxymethylsilylpropylbenzo Thiazolyltetrasulfide, and the like, and any one or a mixture of two or more thereof may be used. Preferably, considering the reinforcing improvement effect, it may be bis (3-triethoxysilylpropyl) polysulfide or 3-trimethoxysilylpropylbenzothiazyl tetrasulfide.

In addition, in the rubber composition according to one embodiment of the present invention, since a modified conjugated diene-based polymer having a functional group having high affinity with silica is introduced as the rubber component, the compounding amount of the silane coupling agent is conventional. The silane coupling agent may be used in an amount of 1 part by weight to 20 parts by weight, or 5 parts by weight to 15 parts by weight with respect to 100 parts by weight of silica, and the effect as a coupling agent is within this range. While sufficiently exhibiting, there is an effect of preventing 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 be specifically sulfur powder, and may be included in an amount of 0.1 parts by weight to 10 parts by weight with respect to 100 parts by weight of the rubber component, while ensuring the required elastic modulus and strength of the vulcanized rubber composition within this range and at the same time low fuel efficiency. Excellent effect.

The rubber composition according to an embodiment of the present invention, in addition to the above components, various additives commonly used in the rubber industry, specifically, vulcanization accelerators, process oils, plasticizers, antioxidants, anti-aging agents, anti-scoring agents, and zinc (zinc) white), stearic acid, a thermosetting resin, or a thermoplastic resin.

The vulcanization accelerator is, for example, a thiazole-based compound such as M (2-mercaptobenzothiazole), DM (dibenzothiazyl disulfide), CZ (N-cyclohexyl-2-benzothiazylsulfenamide), or DPG. Guanidine-based compounds 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 the tensile strength and abrasion resistance, when the aromatic process oil, hysteresis loss and low temperature characteristics are considered. Naphthenic or paraffinic process oils 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 there is an effect of preventing a decrease in 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, dibutylhydroxytoluene, 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) and rubber 0.1 parts by weight to 6 parts by weight based on 100 parts by weight of the component may be used.

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 condensate 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 may be obtained by kneading using a kneading machine such as a Banbury mixer, a roll, an internal mixer, etc. by the compounding formulation, and has low heat resistance and abrasion resistance by a vulcanization process after molding. This excellent rubber composition can be obtained.

Accordingly, the rubber composition may be used for tire members such as tire treads, under treads, sidewalls, carcass coated rubbers, belt coated rubbers, bead fillers, pancreapers, or bead coated rubbers, dustproof rubbers, belt conveyors, hoses, and the like. It may be useful for the production of various industrial rubber products.

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

The tire may include a tire or a tire tread.

Example

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

Example 1

In a first reactor of two reactors connected in series, 15.0 g / h of 1,3-butadiene solution in which 1,3-butadiene was dissolved in 60% by weight of 1,3-butadiene in n-hexane, and 48.3 kg / of n-hexane h, 36.0 g / h of 1,2-butadiene solution in which 1,2-butadiene was dissolved in 2.0% by weight of n-hexane, and N, N, N ', N'-tetramethylethylene in n-hexane as a polar additive. 31.5 g / h of a solution in which diamine was dissolved at 1% by weight and an n-butyllithium solution in which n-butyllithium was dissolved in 10% by weight of n-hexane were injected at a rate of 31.5 g / h as a polymerization initiator. At this time, the temperature of the first reactor was maintained at 65 ℃, when the polymerization conversion rate was 43%, the polymer was transferred from the first reactor to the second reactor through the transfer pipe.

Subsequently, the temperature of the second reactor was maintained at 70 ° C., and the polymerization product was transferred from the second reactor to the blend tank through the transfer pipe when the polymerization conversion rate reached 95%.

During transfer of the polymer from the second reactor to the blend tank, N- (3-1H-imidazol-1-yl) propyl) -3- (triethoxysilyl) -N- (3- (triethoxysilyl) as a modifier ) Propan-1-amine) (N- (3- (1H-imidazol-1-yl) propyl) -3- (triethoxysilyl) -N- (3- (triethoxysilyl) propyl) propan-1-amine) is 20 weight The solution dissolved in% was added at a rate of 111.7 g / h.

Thereafter, IR1520 (BASF, Inc.) solution dissolved in 30% by weight of an antioxidant into the polymerization solution discharged from the second reactor was injected and stirred at a rate of 170 g / h. The resulting polymer was placed in hot water heated with steam and stirred to remove the solvent to prepare a modified conjugated diene polymer.

Example 2

In a first reactor of three reactors connected in series, 15.0 kg / h of 1,3-butadiene solution in which 1,3-butadiene was dissolved in 60% by weight of 1,3-butadiene in n-hexane, and 48.3 kg / of n-hexane h, 36.0 g / h of 1,2-butadiene solution in which 1,2-butadiene was dissolved in 2.0% by weight of n-hexane, and N, N, N ', N'-tetramethylethylene in n-hexane as a polar additive. 31.5 g / h of a solution in which diamine was dissolved at 1% by weight and an n-butyllithium solution in which n-butyllithium was dissolved in 10% by weight of n-hexane in a polymerization initiator were injected at a rate of 47.9 g / h. At this time, the temperature of the first reactor was maintained at 65 ℃, when the polymerization conversion rate was 48%, the polymer was transferred from the first reactor to the second reactor through the transfer pipe.

The temperature of the second reactor was maintained at 70 ° C., and the polymerization product was transferred from the second reactor to the third reactor through a transfer pipe when the polymerization conversion rate reached 95%.

The polymer was transferred from the second reactor to the third reactor, and N, N-bis (3- (diethoxy (methyl) silyl) propyl) -methyl-1-amine (N, N-bis (3- (diethoxy) was used as a modifier. A solution in which (methyl) silyl) propyl) -methyl-1-amine) was dissolved at 20% by weight was added to a third reactor at a rate of 170.0 g / h. The temperature of the third reactor was maintained at 70 ° C.

Thereafter, IR1520 (BASF) solution dissolved at 30% by weight as an antioxidant was injected into the polymerization solution discharged from the third reactor at a rate of 170 g / h and stirred. The resulting polymer was placed in hot water heated with steam and stirred to remove the solvent to prepare a modified conjugated diene polymer.

Example 3

3,3 '-(1,1,3,3-tetramethoxydisiloxane-1,3 instead of N, N-bis (3- (diethoxy (methyl) silyl) propyl) -methyl-1-amine as a modifier -Diyl) bis (N, N-diethylpropan-1-amine) (3,3 '-(1,1,3,3-tetramethoxydisiloxane-1,3-diyl) bis (N, N-diethylpropan-1- A modified conjugated diene-based polymer was prepared in the same manner as in Example 2 except that the solution in which amine) was dissolved at 20 wt% was continuously added to the third reactor at a rate of 135.2 g / h.

Example 4

N- (3,6,9,12-tetraoxahexadecyl) -N- (3- instead of N, N-bis (3- (diethoxy (methyl) silyl) propyl) -methyl-1-amine as a modifier (Triethoxysilyl) propyl) -3,6,9,12-tetraoxahexadecane-1-amine (N- (3,6,9,12-tetraoxahexadecyl) -N- (3- (triethoxysilyl) propyl) -3,6,9,12-tetraoxahexadecan-1-amine) in the same manner as in Example 2 except that the solution dissolved at 20% by weight was continuously added to the third reactor at a rate of 218.7 g / h The modified conjugated diene polymer was prepared.

Example 5

In a first reactor of three reactors connected in series, 15.0 kg / h of 1,3-butadiene solution in which 1,3-butadiene was dissolved in 60% by weight of 1,3-butadiene in n-hexane, and 48.3 kg / of n-hexane h, 36.0 g / h of 1,2-butadiene solution in which 1,2-butadiene was dissolved in 2.0% by weight in n-hexane, and N, N, N ', N' in n-hexane and n-hexane as a polar additive. 31.5 g / h of a solution in which tetramethylethylenediamine was dissolved at 1% by weight, and an n-butyllithium solution in which n-butyllithium was dissolved in 10% by weight of n-hexane as a polymerization initiator at a rate of 58.5 g / h. Injected. At this time, the temperature of the first reactor was maintained at 55 ℃, when the polymerization conversion rate was 43%, the polymer was transferred from the first reactor to the second reactor through a transfer pipe.

The temperature of the second reactor was maintained at 65 ° C, and the polymerization product was transferred from the second reactor to the third reactor through the transfer pipe when the polymerization conversion rate was 95%.

The polymer was transferred from the second reactor to the third reactor, and a solution containing 1,4-bis (3- (triethoxysilyl) propyl) piperazine dissolved as 20% by weight as a modifier was prepared at a rate of 104.4 g / h. 3 reactors. The temperature of the third reactor was maintained at 65 ° C.

Thereafter, IR1520 (BASF) solution dissolved at 30% by weight as an antioxidant was injected into the polymerization solution discharged from the third reactor at a rate of 170 g / h and stirred. The resulting polymer was placed in hot water heated with steam and stirred to remove the solvent to prepare a modified conjugated diene polymer.

Example 6

In a first reactor of two reactors connected in series, 15.0 g / h of 1,3-butadiene solution in which 1,3-butadiene was dissolved in 60% by weight of 1,3-butadiene in n-hexane, and 48.3 kg / of n-hexane h, 36.0 g / h of 1,2-butadiene solution in which 1,2-butadiene was dissolved in 2.0% by weight of n-hexane, and N, N, N ', N'-tetramethylethylene in n-hexane as a polar additive. 98.0 g / h of the solution in which diamine was dissolved at 1% by weight, and n-butyllithium solution in which n-butyllithium was dissolved in 10% by weight of n-hexane in a polymerization initiator were injected at a rate of 31.5 g / h. At this time, the temperature of the first reactor was maintained at 60 ℃, when the polymerization conversion rate was 41%, the polymer was transferred from the first reactor to the second reactor through a transfer pipe.

At this time, the temperature of the second reactor was maintained to 70 ℃, when the polymerization conversion rate was 95% through the transfer pipe, the polymer was transferred to the blend tank from the second reactor.

During the transfer of the polymer to the blend tank in the second reactor, 8,8-dibutyl-3,13-dimethoxy-3,13-dimethyl-2,14-dioxa-7,9-dithia-3, 13-disila-8-stanpentanecane (8,8-dibutyl-3,13-dimethoxy-3,13-dimethyl-2,14-dioxa-7,9-dithia-3,13-disila-8-stannapentadecane ) Was added at a rate of 123.8 g / h.

Thereafter, IR1520 (BASF) solution dissolved at 30% by weight as an antioxidant was injected into the polymerization solution discharged from the second reactor at a rate of 170 g / h and stirred. The resulting polymer was placed in hot water heated with steam and stirred to remove the solvent to prepare a modified conjugated diene polymer.

Example 7

In a first reactor of three reactors connected in series, 15.0 kg / h of 1,3-butadiene solution in which 1,3-butadiene was dissolved in 60% by weight of 1,3-butadiene in n-hexane, and 48.3 kg / of n-hexane h, 36.0 g / h of 1,2-butadiene solution in which 1,2-butadiene was dissolved in 2.0% by weight of n-hexane, and N, N, N ', N'-tetramethylethylene in n-hexane as a polar additive. 102.0 g / h of a solution in which diamine was dissolved at 1% by weight, and an n-butyllithium solution in which n-butyllithium was dissolved in 10% by weight of n-hexane in a polymerization initiator was injected at a rate of 47.9 g / h. At this time, the temperature of the first reactor was maintained at 60 ℃, when the polymerization conversion rate was 45%, the polymer was transferred from the first reactor to the second reactor through a transfer pipe.

The temperature of the second reactor was maintained at 70 ℃, and when the polymerization conversion rate was 95% through the transfer pipe, the polymer was transferred from the second reactor to the third reactor.

Transfer the polymer from the second reactor to the third reactor, N- (3,6,9,12-tetraoxahexadecyl) -N- (3- (triethoxysilyl) propyl) -3.6.9.12- as a modifier A solution in which tetraoxahexadecane-1-amine was dissolved at 20% by weight was added to a third reactor at a rate of 218.7 g / h. The temperature of the third reactor was maintained at 70 ° C.

Thereafter, IR1520 (BASF, Inc.) solution dissolved at 30% by weight as an antioxidant in the polymerization solution discharged from the third reactor was injected and stirred at a rate of 170 g / h. The resulting polymer was placed in hot water heated with steam and stirred to remove the solvent to prepare a modified conjugated diene polymer.

Example 8

Instead of N- (3,6,9,12-tetraoxahexadecyl) -N- (3- (triethoxysilyl) propyl) -3,6,9,12-tetraoxahexadecane-1-amine as a modifier To a solution in which 3,3 '-(1,1,3,3, -tetramethoxydisiloxane-1,3-diyl) bis (N, N-diethylpropan-1-amine) was dissolved in 20 wt% A modified conjugated diene-based polymer was prepared in the same manner as in Example 7, except that the mixture was continuously added to a third reactor at a rate of 135.2 g / h.

Example 9

In a first reactor of three reactors connected in series, 15.0 kg / h of 1,3-butadiene solution in which 1,3-butadiene was dissolved in 60% by weight of 1,3-butadiene in n-hexane, and 48.3 kg / of n-hexane h, 36.0 g / h of 1,2-butadiene solution in which 1,2-butadiene was dissolved in 2.0% by weight of n-hexane, and 2,2-di (2-tetrahydrofuryl) propane in n-hexane as a polar additive. 51.0 g / h of the solution dissolved at 1% by weight and n-butyllithium solution in which n-butyllithium was dissolved at 10% by weight in n-hexane were injected at a rate of 47.9 g / h. At this time, the temperature of the first reactor was maintained to 50 ℃, when the polymerization conversion rate was 42%, the polymer was transferred from the first reactor to the second reactor through a transfer pipe.

The temperature of the second reactor was maintained at 60 ° C., and the polymerization product was transferred from the second reactor to the third reactor through a transfer pipe when the polymerization conversion rate reached 95%.

Transfer the polymer from the second reactor to the third reactor, N, N-diethyl-3- (triethoxysilyl) propan-1-amine (N, N-diethyl-3- (triethoxysilyl) propan-1) as a modifier -amine) was added to the third reactor at a rate of 88.2 g / h. The temperature of the third reactor was maintained at 60 ° C.

Thereafter, IR1520 (BASF, Inc.) solution dissolved at 30% by weight as an antioxidant in the polymerization solution discharged from the third reactor was injected and stirred at a rate of 170 g / h. The resulting polymer was placed in hot water heated with steam and stirred to remove the solvent to prepare a modified conjugated diene polymer.

Example 10

N, N-bis (3- (diethoxy (methyl) silyl) propyl) -methyl-1-amine is used instead of N, N-diethyl-3- (triethoxysilyl) propan-1-amine as a modifier. A modified conjugated diene-based polymer was prepared in the same manner as in Example 9 except that the solution dissolved in wt% was continuously added to the third reactor at a rate of 120.0 g / h.

Comparative Example 1

In a first reactor of three reactors connected in series, 15.0 kg / h of 1,3-butadiene solution in which 1,3-butadiene was dissolved in 60% by weight of 1,3-butadiene in n-hexane, and 48.3 kg / of n-hexane h, 36.0 g / h of 1,2-butadiene solution in which 1,2-butadiene was dissolved in 2.0% by weight of n-hexane, and N, N, N ', N'-tetramethylethylene in n-hexane as a polar additive. 31.5 g / h of a solution in which diamine was dissolved at 1% by weight and an n-butyllithium solution in which n-butyllithium was dissolved in 10% by weight of n-hexane in a polymerization initiator were injected at a rate of 58.5 g / h. At this time, the temperature of the first reactor was maintained at 55 ° C, and when the polymerization conversion rate was 46%, the polymer was transferred from the first reactor to the second reactor through a transfer pipe.

The temperature of the second reactor was maintained at 65 ° C, and the polymerization product was transferred from the second reactor to the third reactor through the transfer pipe when the polymerization conversion rate was 95%.

The polymer was transferred from the second reactor to the third reactor, and a solution in which tetrachlorosilane was dissolved in n-hexane as a modifier at 20 wt% was continuously introduced into the third reactor at a rate of 50.3 g / h. The temperature of the third reactor was maintained at 65 ° C.

Thereafter, IR1520 (BASF) solution dissolved at 30% by weight as an antioxidant was injected into the polymerization solution discharged from the third reactor at a rate of 170 g / h and stirred. The resulting polymer was placed in hot water heated with steam and stirred to remove the solvent to prepare a modified conjugated diene polymer.

Comparative Example 2

The reaction temperature is maintained at 75 ° C. in the first reactor, 85 ° C. in the second reactor, and 85 ° C. in the third reactor, and when the polymerization conversion rate reaches 70%, the polymer is transferred from the first reactor to the second reactor through a transfer pipe. In the third reactor, a solution of 1,4-bis (3- (triethoxysilyl) propyl) piperazine dissolved in 20% by weight of n-hexane was added to the third reactor at a rate of 104.4 g / h. A modified conjugated diene-based polymer was prepared in the same manner as in Comparative Example 1 except that the polymerization was carried out.

Comparative Example 3

1000 g of 1,3 butadiene and 5000 g of normal hexane and 0.3 g of N, N, N ', N'-tetramethylethylenediamine were added to a 20 L autoclave reactor, and the temperature inside the reactor was raised to 50 ° C. When the internal temperature of the reactor reached 40 ° C, 4.4 mmol of n-butyllithium was added to the reactor to perform an adiabatic heating reaction. After 25 minutes, 4.4 mmol of N, N-bis (3- (diethoxy (methyl) silyl) propyl) -methyl-1-amine was added and the mixture was denatured for 15 minutes. Thereafter, the polymerization reaction was stopped using ethanol, and 45 ml of a solution in which 0.35% by weight of IR1520 (BASF) was dissolved in hexane was added as an antioxidant. The resulting polymer was placed in hot water heated with steam and stirred to remove the solvent to prepare a modified conjugated diene polymer.

Comparative Example 4

The reaction temperature is maintained at 85 ° C. in the first reactor, 75 ° C. in the second reactor, and 70 ° C. in the third reactor, and when the polymerization conversion rate is 68%, the polymer is transferred from the first reactor to the second reactor through a transfer pipe. A modified conjugated diene-based polymer was prepared in the same manner as in Example 3 except that the polymer was transferred and polymerized.

Comparative Example 5

Except for adding 1,4'-bis (3- (triethoxysilyl) propyl) piperazine as a denaturant, a solution in which tetrachlorosilane was dissolved at 20% by weight was added at a rate of 50.3 g / h. Was carried out in the same manner as in Example 7, to prepare a modified conjugated diene-based polymer.

Comparative Example 6

The reaction temperature is maintained at 75 ° C. in the first reactor, 75 ° C. in the second reactor, and 70 ° C. in the third reactor, and when the polymerization conversion rate is 68%, the polymer is transferred from the first reactor to the second reactor through a transfer pipe. A modified conjugated diene-based polymer was prepared in the same manner as in Example 8 except that the polymer was transferred and polymerized.

Comparative Example 7

A modified conjugated diene-based polymer was prepared using a continuous reactor in which one polymerization reactor and one modified reactor were connected in series.

Specifically, in a polymerization reactor (first reactor), a 1,3-butadiene solution in which 1,3-butadiene is dissolved in 60 wt% of n-hexane is 15.0 kg / h, n-hexane 48.3 kg / h, n- 36.0 g / h of a 1,2-butadiene solution in which 1,2-butadiene was dissolved in 2.0% by weight of hexane, and 1% by weight of 2,2-di (2-tetrahydrofuryl) propane in n-hexane as a polar additive. The solution of n-butyllithium in which 51.0 g / h of the solution dissolved in 10% by weight of n-butyllithium was dissolved in n-hexane as a polymerization initiator was injected at a rate of 47.9 g / h.

At this time, the temperature of the polymerization reactor was maintained at 50 ℃, when the polymerization conversion rate was 95%, the polymer was transferred from the polymerization reactor to the modified reactor (second reactor) through the transfer pipe.

120.0 g / h of a solution in which N, N-bis (3- (diethoxy (methyl) silyl) propyl) -methyl-1-amine was dissolved at 20% by weight as a modifier during transfer of the polymer from the polymerization reactor to the modification reactor. Was added at the rate of. At this time, the temperature of the modified reactor was maintained to 60 ℃, through the transfer pipe, the polymer was transferred to the blend tank in the second reactor.

Then, IR1520 (BASF Co., Ltd.) solution dissolved in 30 wt% as an antioxidant in the polymerization solution discharged into the blend tank was injected and stirred at a rate of 170 g / h. The resulting polymer was placed in hot water heated with steam and stirred to remove the solvent to prepare a modified conjugated diene polymer.

Experimental Example

Experimental Example 1

For each of the modified or unmodified conjugated diene polymers prepared in Examples and Comparative Examples, the styrene unit and vinyl content in the conjugated diene polymer, the weight average molecular weight (Mw, X10 ³ g / mol), and the number average molecular weight ( Mn, X10 ³ g / mol), molecular weight distribution (PDI; MWD), Mooney viscosity (MV), and Si content were measured, respectively. The results are shown in Tables 1 and 2 below.

1) styrene unit and vinyl content

Styrene units (SM, wt%) and vinyl content (Vinyl, wt%) in the modified conjugated diene-based polymer were measured and analyzed using Varian VNMRS 500 MHz NMR.

When NMR was measured, 1,1,2,2-tetrachloroethane was used, and the solvent peak was calculated to 5.97 ppm, 7.2 to 6.9 ppm random styrene, 6.9 to 6.2 ppm block styrene, and 5.8 to 5.1 ppm Styrene units and vinyl content were calculated using 1,4-vinyl and 5.1 to 4.5 ppm as peaks of 1,2-vinyl.

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

The weight average molecular weight (Mw) and the number average molecular weight (Mn) were measured by gel permeation chromatograph (GPC) analysis, and molecular weight distribution (PDI; MWD; Mw / Mn) was calculated from the respective measured molecular weights. Specifically, the GPC used a combination of two PLgel Olexis (Polymer Laboratories Co.) column and one PLgel mixed-C (Polymer Laboratories Co.) column, all of the newly replaced column was a mixed bed column, The GPC standard material was calculated using polystyrene (PS) when calculating the molecular weight. GPC measurement solvent was prepared by mixing 2 wt% of an amine compound with tetrahydrofuran. At this time, the obtained molecular weight distribution curve is shown in Figs.

3) Mooney viscosity

The Mooney viscosity (MV, (ML1 + 4, @ 100 ℃) MU) was measured using a Rotor Speed 2 ± 0.02 rpm, Large Rotorfmf at 100 ℃ using MV-2000 (ALPHA Technologies, Inc.), the sample used After leaving at room temperature (23 ± 3 ℃) for 30 minutes or more, 27 ± 3 g was collected and filled into the die cavity, and the platen was operated for 4 minutes.

4) Si content

The Si content was measured using an inductively coupled plasma luminescence analyzer (ICP-OES; Optima 7300DV) for ICP analysis. In the case of using the inductively coupled plasma luminescence analyzer, about 0.7 g of the sample was placed in a platinum crucible (Pt crucible), about 1 mL of concentrated sulfuric acid (98 wt%, Electronic grade) was heated at 300 ° C. for 3 hours, and the sample was After the conversation in the electric furnace (Thermo Scientific, Lindberg Blue M) in the program of steps 1 to 3,

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

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

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

1 mL of concentrated nitric acid (48% by weight) and 20 μl of concentrated hydrofluoric acid (50% by weight) were added, the crucible was sealed and shaken for at least 30 minutes, and then 1 mL of boric acid was added to the sample. The mixture was stored at 0 ° C. for at least 2 hours, diluted with 30 mL of ultrapure water, and measured by incubation.

division		Example					Comparative example
		One	2	3	4	5	One	2	3	4
Reaction condition	Reactor number	2	3	3	3	3	3	3	arrangement	3
	Polar additives	TMEDA	TMEDA	TMEDA	TMEDA	TMEDA	TMEDA	TMEDA	TMEDA	TMEDA
	Denaturant	A	B	C	D	F	H	F	B	C
	M: PA	1: 0.05					1: 0.5	1: 0.05	1: 3	1: 0.05
	M: PI	1: 1					0.1: 1	1: 1
	First reactor temperature (° C.)	65	65	65	65	55	55	75	50-> 75	85
	First reactor polymerization conversion (%)	43	48	48	48	43	46	70	-	68
NMR (% by weight)	SM	-	-	-	-	-	-	-	-	-
	Vinyl	10	10	10	10	10	10	10	10	10
GPC	Mw (X10 3 g / mol)	583	352	371	356	537	893	781	505	481
	Mn (X10 3 g / mol)	351	230	231	230	351	350	350	351	230
	PDI	1.66	1.53	1.61	1.55	1.53	2.55	2.23	1.44	2.09
Mooney viscosity (MV)		77	44	34	39	40	43	45	44	35
Si content (ppm)		250	191	219	190	230	23	121	179	220

division		Example					Comparative example
		6	7	8	9	10	5	6	7
Reaction condition	Reactor number	2	3	3	3	3	3	3	2
	Polar additives	TMEDA	TMEDA	TMEDA	DTP	DTP	TMEDA	TMEDA	DTP
	Denaturant	E	D	C	G	B	H	C	B
	M: PA	1: 0.97			1: 0.55		1: 9.7	1: 0.97	1: 0.55
	M: PI	1: 1					0.1: 1	1: 1
	First reactor temperature (° C.)	60	60	60	50	50	60	75	50
	First reactor polymerization conversion (%)	41	45	45	42	42	45	74	95
NMR (% by weight)	SM	-	-	-	-	-	-	-	-
	Vinyl	40	40	40	40	40	40	40	40
GPC	Mw (X10 3 g / mol)	585	338	374	329	345	945	490	511
	Mn (X10 3 g / mol)	350	230	232	230	230	350	230	230
	PDI	1.67	1.47	1.61	1.43	1.50	2.70	2.13	2.22
Mooney viscosity (MV)		40	33	35	34	31	42	44	37
Si content (ppm)		240	201	220	161	209	40	154	190

In Table 1 and Table 2, specific materials and use ratios of the polar additive and the modifier are as follows.

* M: PA = molar ratio of denaturant and polar additive

* M: PI = molar ratio of denaturing agent and polymerization initiator (act.Li)

* DTP: 2,2-di (2-tetrahydrofuryl) propane

* TMEDA: N, N, N ', N'-tetramethylethylenediamine

Modifier A: N- (3-1H-imidazol-1-yl) propyl) -3- (triethoxysilyl) -N- (3- (triethoxysilyl) propan-1-amine)

Modifier B: N, N-bis (3- (diethoxy (methyl) silyl) propyl) -methyl-1-amine

Modifier C: 3,3 '-(1,1,3,3-tetramethoxydisiloxane-1,3-diyl) bis (N, N-diethylpropan-1-amine)

Modifier D: N- (3,6,9,12-tetraoxahexadecyl) -N- (3- (triethoxysilyl) propyl) -3,6,9,12-tetraoxahexadecane-1- Amine

Modifier E: 8,8-dibutyl-3,13-dimethoxy-3,13-dimethyl-2,14-dioxa-7,9-dithia-3,13-disila-8-stanpentanedecane

Modifier F: 1,4-bis (3- (triethoxysilyl) propyl) piperazine

Modifier G: N, N-diethyl-3- (triethoxysilyl) propan-1-amine

Modifier H: tetrachlorosilane

As shown in Table 1 and Table 2, the modified conjugated diene-based polymer of Examples 1 to 10 according to an embodiment of the present invention has a unimodal form molecular weight distribution curve by gel permeation chromatography (See FIG. 1 and FIG. 2) Both PDI (molecular weight distribution) was found to be less than 1.7, Si content is more than 100 ppm. On the other hand, the modified conjugated diene-based polymers of Comparative Example 1, Comparative Example 2 and Comparative Examples 4 to 7 all had a PDI of more than 1.7, and the modified conjugated diene-based polymer of Comparative Example 3 had a molecular weight by gel permeation chromatography. The distribution curve showed trimodal morphology (see Figure 3).

Experimental Example 2

In order to compare and analyze the physical properties of the rubber composition and the molded article prepared from each modified or unmodified conjugated diene-based copolymer prepared in Examples and Comparative Examples, the tensile and viscoelastic properties were measured and the results Table 4 and Table 5 below.

1) Preparation of Rubber Specimen

Each modified or unmodified conjugated diene-based polymer of Examples and Comparative Examples was blended under the blending conditions shown in Table 3 below as a raw material rubber. The raw materials in Table 3 are each parts by weight based on 100 parts by weight of rubber.

division	Raw material	Content (parts by weight)
1st stage kneading	Rubber	100
	Silica	70
	Coupling Agent (X50S)	11.2
	Process oil	37.5
	Galvanizing agent	3.0
	Stearic acid	2.0
	Antioxidant	2.0
	Anti aging agents	2.0
	Wax	1.0
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, the raw rubber, silica (filler), organosilane coupling agent, process oil, galvanizing agent, stearic acid, antioxidant, antioxidant and wax were kneaded using a half-variety mixer equipped with a temperature controller. At this time, the initial temperature of the kneader was controlled at 70 ° C., and the primary compound was obtained at the discharge temperature of 145 ° C. to 155 ° C. after the completion of the mixing. In the second stage kneading, after cooling the said primary compound to room temperature, the primary compound, sulfur, a rubber accelerator, and a vulcanization accelerator were added to the kneader, and it mixed at the temperature of 100 degrees C or less, and obtained the secondary compound. Thereafter, rubber specimens were prepared through a curing process at 160 ° C. for 20 minutes.

2) tensile properties

Tensile properties were prepared in accordance with the tensile test method of ASTM 412 and measured the tensile strength at the cutting of the test piece and the tensile stress (300% modulus) at 300% elongation. Specifically, the 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

Viscoelastic properties were determined by measuring the viscoelastic behavior for dynamic deformation at 10 Hz frequency and each measurement temperature (-60 ℃ ~ 60 ℃) in the film tension mode using a dynamic mechanical analyzer (GABO). The higher the index value of low temperature 0 ℃ tan δ in the results, the better the wet road resistance, and the higher the index value of high temperature 60 ℃ tan δ, the lower the hysteresis loss and the lower running resistance (fuelability). In this case, the result values of Examples 1 to 5 and Comparative Examples 2 to 4 were expressed by indexing the result value of Comparative Example 1 to 100, Examples 6 to 10, Comparative Example 6 and Comparative Examples Each result value of 7 was shown exponentially as the result value of the comparative example 5 as 100.

4) Machinability Characteristics

1) The pattern viscosity (MV, (ML1 + 4, @ 100 ℃) MU) of the secondary compound obtained when preparing the rubber specimens were measured to compare and analyze the processability characteristics of each polymer, wherein the lower the Mooney viscosity measured value It is excellent in workability characteristics.

Specifically, using the MV-2000 (ALPHA Technologies, Inc.) at 100 ℃ Rotor Speed 2 ± 0.02 rpm, using a Large Rotor, each secondary blend was left at room temperature (23 ± 3 ℃) for 30 minutes or more 27 ± 3 g was taken and filled into the die cavity and platen operated for 4 minutes.

division		Example					Comparative example
		One	2	3	4	5	One	2	3	4
Machinability Characteristics		74	62	63	66	71	73	73	85	69
Tensile Properties	Tensile strength (kgf / cm 2 , index)	208	202	206	205	200	188	190	201	197
	300% modulus (kgf / cm 2 , index)	65	59	62	62	57	35	50	60	54
Viscoelastic properties	tan δ (at 0 ° C, Index)	104	103	105	105	103	100	101	103	101
	tan δ (at 60 ° C, Index)	128	124	131	130	123	100	111	112	110

division		Example					Comparative example
		6	7	8	9	10	5	6	7
Machinability Characteristics		66	59	62	63	60	74	72	68
Tensile Properties	Tensile strength (kgf / cm 2 )	201	208	209	206	205	189	204	200
	300% modulus (kgf / cm 2 )	57	63	64	59	60	37	60	57
Viscoelastic properties	tan δ (at 0 ° C, Index)	101	105	105	103	104	100	105	104
	tan δ (at 60 ° C, Index)	120	124	125	122	121	100	110	107

As shown in Table 4 and Table 5, Examples 1 to 10 according to an embodiment of the present invention was confirmed that the tensile properties, viscoelastic properties and workability properties compared to Comparative Examples 1 to 7.

On the other hand, in the viscoelastic properties, it is known that it is very difficult to have a characteristic in which the tan δ value at 0 ° C is usually improved while the tan δ value at 60 ° C is improved. Therefore, Examples 1 to 10, which show a significant improvement in tan δ value at 60 ° C. while having a good level of tan δ at 0 ° C. compared to Comparative Examples 1 to 7, have very good viscoelastic properties. It can be seen that.

Claims (10)

1. The molecular weight distribution curve by gel permeation chromatography (GPC) has a unimodal form,

   Molecular weight distribution (PDI; MWD) is less than 1.7,

   A modified conjugated diene polymer having a Si content of 100 ppm or more by weight.
2. The method of claim 1,

   The modified conjugated diene-based polymer is a modified conjugated diene-based polymer comprising a repeating unit derived from a conjugated diene-based monomer and a modifier-derived functional group.
3. The method of claim 2,

   The modifier is a modified conjugated diene polymer of the alkoxy silane-based modifier.
4. The method of claim 1,

   The modified conjugated diene-based polymer is a modified conjugated diene-based polymer having a number average molecular weight (Mn) of 1,000 g / mol to 2,000,000 g / mol, and a weight average molecular weight (Mw) of 1,000 g / mol to 3,000,000 g / mol.
5. The method of claim 1,

   The molecular weight distribution (PDI; MWD) is from 1.0 to less than 1.7 modified conjugated diene-based polymer.
6. The method of claim 1,

   The modified conjugated diene-based polymer is modified conjugated diene-based polymer having a Mooney viscosity (Mooney viscosity) at 30 ℃ or more.
7. In standard polystyrene reduced molecular weight by gel permeation chromatography, the polymer component having a molecular weight of 100,000 g / mol or more is unimodal,

   Molecular weight distribution (PDI; MWD) is 2.0 or less,

   The number average molecular weight (Mn) is from 250,000 g / mol to 700,000 g / mol,

   The vinyl content of the butadiene unit is 20 mol% to 80 mol% or less,

   Si content is at least 100 ppm by weight,

   Modified conjugated diene polymer whose content of the polymer component which has a functional group is 50 weight% or more.
8. A rubber composition comprising the modified conjugated diene-based polymer and the filler according to claim 1.
9. The method of claim 8,

   The rubber composition comprises 0.1 part by weight to 200 parts by weight of a filler based on 100 parts by weight of the modified conjugated diene-based polymer.
10. The method of claim 9,

    The filler is a silica-based filler or a carbon black-based filler rubber composition.

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