KR102059670B1 - Modifying agent, preparation method of modified conjugated diene polymer using the modifying agent and modified conjugated diene polymer - Google Patents

Abstract

The present invention provides a rubber modifier compound, a method for producing a modified conjugated diene-based polymer using the same, a modified conjugated diene-based polymer prepared from the production method, a rubber composition comprising the modified conjugated diene-based polymer and a tire prepared from the rubber composition It is about. Accordingly, the rubber modifier compound may be used as a modifier for rubber, in particular, a conjugated diene-based polymer, to be bonded to the conjugated diene-based polymer chain to easily introduce a filler affinity functional group. Therefore, the modified conjugated diene-based polymer prepared using the rubber modifier compound may have excellent affinity with the filler, and as a result, the processed article (eg, tire) manufactured from the rubber composition including the polymer may have a tensile strength, Abrasion resistance and wet road resistance properties may be excellent.

Description

Modifying agent, preparation method of modified conjugated diene polymer using the modifying agent and modified conjugated diene polymer

The present invention provides a rubber modifier compound, a method for producing a modified conjugated diene-based polymer using the same, a modified conjugated diene-based polymer prepared from the production method, a rubber composition comprising the modified conjugated diene-based polymer and a tire prepared from the rubber composition It is about.

In recent years, 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 properties, and adjusting stability represented by wet skid resistance.

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 heating and the like are used. That is, a rubber material having a high rebound elasticity at the above temperature or a small tan δ or 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 skid resistance. Recently, conjugated diene-based (co) polymers 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 adjusted by coupling or modification. It can be adjusted. Therefore, it is easy to change the structure of the final manufactured SBR or BR rubber, and the movement of the chain ends can be reduced by the binding or modification of the chain ends, and the bonding strength with fillers such as silica or carbon black can be increased. It is widely used as a rubber material for tires.

When the solution-polymerized SBR is used as a rubber material for tires, the vinyl content in the SBR is increased to increase the glass transition temperature of the rubber, thereby controlling tire required properties such as running resistance and braking force, and properly adjusting the glass transition temperature. By adjusting the fuel consumption can be reduced.

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, a monofunctional initiator, using a binder such as a tin compound. It was.

Meanwhile, carbon black and silica are used as reinforcing fillers for tire treads. When silica is used as reinforcing fillers, low hysteresis loss and wet skid resistance are improved. However, the hydrophilic surface silica has a disadvantage of poor dispersibility due to low affinity with rubber compared to the hydrophobic surface carbon black, so that a separate silane coupler may be used to improve dispersibility or to impart a bond between silica and rubber. It is necessary to use a ring agent.

Thus, a method of introducing a functional group having affinity or reactivity with silica to the rubber molecule terminal portion, but the effect is not sufficient.

Therefore, there is a need for development of a rubber having high affinity with fillers including silica.

US 4,397,994 A

The present invention has been made to solve the problems of the prior art, an object of the present invention is to provide a compound for a rubber modifier that can provide a filler, in particular a silica-based filler affinity functional group.

Another object of the present invention is to provide a modified conjugated diene-based polymer comprising a functional group derived from the compound for the rubber modifier.

Another object of the present invention to provide a method for producing a modified conjugated diene polymer using the compound for the rubber modifier.

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

Furthermore, another object of the present invention is to provide a tire made from the rubber composition.

In order to solve the above problems, a compound represented by the following formula (1) is provided.

Compound represented by the following formula (1):

[Formula 1]

In Chemical Formula 1,

R ₁ to R ₃ are each independently Alkyl having 1 to 20 carbon atoms,

A and B are independently of each other alkylene having 1 to 20 carbon atoms.

In addition, the present invention provides a modified conjugated diene-based polymer comprising a functional group derived from the compound represented by the formula (1).

In addition, the present invention is to prepare an active polymer in which the alkali metal is bonded to at least one terminal by polymerizing a conjugated diene monomer or an aromatic vinyl monomer and a conjugated diene monomer in the presence of an organic alkali metal compound in a hydrocarbon solvent (step 1 ); And it provides a method for producing a modified conjugated diene-based polymer comprising the step (step 2) of reacting the active polymer with the compound represented by the formula (1).

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

Furthermore, there is provided a tire made from the rubber composition.

Compound represented by the formula (1) according to the present invention can be used as a modifier for rubber, in particular conjugated diene-based polymer, it is coupled to the conjugated diene-based polymer chain can be easily introduced filler affinity functional group.

In addition, the modified conjugated diene-based polymer according to the present invention may be excellent in affinity with the filler, in particular, silica-based filler by binding a functional group, such as a siloxane group and an amine group represented by the formula (1) in the polymer chain.

In addition, the production method according to the present invention can easily prepare a modified conjugated diene-based polymer having excellent modification rate by using the compound represented by the formula (1).

In addition, the rubber composition according to the present invention may be excellent in workability by including a modified conjugated diene-based polymer having excellent affinity with the filler, and as a result, the processed product (for example, a tire) manufactured using the rubber composition may be tensile. Strength, wear resistance and wet road resistance properties may be excellent.

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

The terms or words used in this specification and claims are not to be construed as limiting in their usual or dictionary meanings, and the inventors may appropriately define the concept of terms in order to best describe their invention. It should be interpreted as meaning and concept corresponding to the technical idea of the present invention based on the principle that the present invention.

The present invention provides a compound for rubber modifiers that can provide an affinity functional group with reinforcing fillers, especially silica based fillers.

The compound according to an embodiment of the present invention is characterized by represented by the following formula (1).

Compound represented by the following formula (1):

[Formula 1]

In Chemical Formula 1,

R ₁ to R ₃ are each independently Alkyl having 1 to 20 carbon atoms,

A and B are independently of each other alkylene having 1 to 20 carbon atoms.

Specifically, in Formula 1, R ₁ to R ₃ are independently of each other. Alkyl having 1 to 10 carbon atoms, A and B may be independently alkylene having 1 to 10 carbon atoms.

In addition, in Formula 1, R ₁ to R ₃ are independently of each other. Alkyl having 1 to 6 carbon atoms, A and B may be independently alkylene having 1 to 6 carbon atoms.

More specifically, Chemical Formula 1 may be represented by the following Chemical Formula 2.

[Formula 2]

In addition, the compound represented by Formula 1 may be a rubber modifier as described above.

Specifically, the compound represented by Formula 1 may be a modifier for conjugated diene polymer. Herein, the conjugated diene polymer may be a conjugated diene monomer homopolymer or a copolymer of a conjugated diene monomer and an aromatic vinyl monomer.

In addition, the present invention provides a modified conjugated diene-based polymer comprising a functional group derived from the compound represented by the following formula (1).

[Formula 1]

In Chemical Formula 1,

R ₁ to R ₃ are each independently Alkyl having 1 to 20 carbon atoms,

A and B are independently of each other alkylene having 1 to 20 carbon atoms.

The modified conjugated diene-based polymer according to an embodiment of the present invention includes a functional group derived from the compound represented by Formula 1, the modified conjugated diene-based polymer may be modified by a compound represented by Formula 1.

The modified conjugated diene-based polymer has a siloxane group and an amine group bonded to the polymer chain may be excellent in affinity with the filler, in particular silica filler. Accordingly, the physical properties of the rubber composition including the modified conjugated diene-based polymer may be excellent, and consequently, the tensile strength of a molded article, such as a tire, manufactured using the rubber composition may be excellent. Abrasion resistance and wet road resistance can be improved.

In addition, the modified conjugated diene-based polymer may have a number average molecular weight of 1,000 g / mol to 2,000,000 g / mol, specifically 10,000 g / mol to 1,000,000 g / mol.

The modified conjugated diene-based polymer may have a weight average molecular weight of 10,000 g / mol to 3,000,000 g / mol, specifically may be 100,000 g / mol to 2,000,000 g / mol.

The modified conjugated diene-based polymer may be a polydispersity index of 0.5 to 10, specifically 1 to 4.

In addition, the modified conjugated diene-based polymer may have a vinyl content of 5% by weight or more, specifically 10% by weight or more, more specifically 10% by weight to 50% by weight, and the glass transition temperature when the vinyl content is in the above range. Can be adjusted to an appropriate range, and when applied to a tire, not only the properties required for the tire such as driving resistance and braking force are excellent, but also it has an effect of reducing fuel consumption.

In this case, the vinyl content represents the content of the 1,2-added conjugated diene monomer instead of 1,4-addition based on 100% by weight of the conjugated diene polymer composed of a monomer having a vinyl group or a conjugated diene monomer.

In addition, the present invention provides a method for producing a modified conjugated diene-based polymer using the compound represented by the formula (1).

The production method according to an embodiment of the present invention is an active polymer in which an alkali metal is bonded to at least one terminal by polymerizing a conjugated diene monomer or an aromatic vinyl monomer and a conjugated diene monomer in the presence of an organic alkali metal compound in a hydrocarbon solvent. Preparing (step 1); And reacting the active polymer with the compound represented by Chemical Formula 1 (step 2).

Step 1 is a step for preparing an active polymer having an alkali metal bonded to at least one end thereof, which is performed by polymerizing a conjugated diene monomer or a conjugated diene monomer and an aromatic vinyl monomer in the presence of an organic alkali metal compound in a hydrocarbon solvent. Can be.

The polymerization of step 1 may be to use a conjugated diene monomer alone or a conjugated diene monomer and an aromatic vinyl monomer together as a monomer. That is, the polymer prepared by the above production method according to an embodiment of the present invention may be a homopolymer derived from a conjugated diene monomer or a copolymer derived from a conjugated diene monomer and an aromatic vinyl monomer.

When the modified conjugated diene polymer is a copolymer of a conjugated diene monomer and an aromatic vinyl monomer, the copolymer may be a random copolymer.

Here, the "random copolymer" may indicate that the structural units constituting the copolymer are randomly arranged.

The conjugated diene monomer is not particularly limited, but for example, 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, piperylene, 3-butyl-1,3-octadiene, isoprene and 2-phenyl It may be one or more selected from the group consisting of -1,3-butadiene.

When the conjugated diene-based monomer and the aromatic vinyl monomer are used together as the monomer, the conjugated diene-based monomer is 60 wt% or more, specifically, in the finally prepared modified conjugated diene-based polymer. 60 wt% to 90 wt%, more specifically, 60 wt% to 85 wt%.

The aromatic vinyl monomer is not particularly limited, but for example, styrene, α-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 1-vinylnaphthalene, 4-cyclohexylstyrene, 4- (p It may be one or more selected from the group consisting of -methylphenyl) styrene and 1-vinyl-5-hexylnaphthalene.

When the conjugated diene monomer and the aromatic vinyl monomer are used together as the monomer, the aromatic vinyl monomer may be 40% by weight or less of the aromatic vinyl monomer-derived unit in the finally prepared modified conjugated diene polymer. It may be used in an amount comprised from 10% by weight to 40% by weight, more specifically 15% by weight to 40% by weight.

Herein, the "derived unit" may refer to a component, a structure, or the substance itself resulting from a substance.

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

The organoalkali metal compound may be used in an amount of 0.01 mmol to 10 mmol based on 100 g of the total monomer.

 The organoalkali metal compound is not particularly limited, but for example, methyllithium, ethyllithium, propyllithium, n-butyllithium, s-butyllithium, t-butyllithium, hexyllithium, n-decyllithium, t-octylithium, Phenyllithium, 1-naphthyllithium, n-eicosilium, 4-butylphenyllithium, 4-tolyllithium, cyclohexyllithium, 3,5-di-n-heptylcyclohexyllithium, 4-cyclopentyllithium, naph At least one member selected from the group consisting of sodium sodium, naphthyl potassium, lithium alkoxide, sodium alkoxide, potassium alkoxide, lithium sulfonate, sodium sulfonate, potassium sulfonate, lithium amide, sodium amide, potassium amide, lithium isopropylamide Can be.

The polymerization of step 1 may be performed by further adding a polar additive as needed, the polar additive may be added to 0.001 parts by weight to 50 parts by weight based on 100 parts by weight of the total monomer. Specifically, the content may be added in an amount of 0.001 part by weight to 10 parts by weight, more specifically 0.005 part by weight to 0.1 part by weight, based on 100 parts by weight of the total monomer.

The polar additives include tetrahydrofuran, ditetrahydrofurylpropane, diethyl ether, cycloamal ether, dipropyl ether, ethylene dimethyl ether, ethylene dimethyl ether, diethyl glycol, dimethyl ether, tertiary butoxyethoxyethane, bis It may be one or more selected from the group consisting of (3-dimethylaminoethyl) ether, (dimethylaminoethyl) ethyl ether, trimethylamine, triethylamine, tripropylamine and tetramethylethylenediamine.

In the manufacturing method according to an embodiment of the present invention, when the conjugated diene-based monomer and the aromatic vinyl-based monomer are copolymerized by using the polar additive, the reaction rate can be easily compensated for by forming a random copolymer. Can be induced.

The polymerization of step 1 may be carried out through an elevated temperature polymerization, or may be carried out through constant temperature polymerization.

The polymerization may be performed at a temperature range of -20 ° C to 200 ° C, specifically 0 ° C to 150 ° C, and more specifically 10 ° C to 120 ° C.

Step 2 is a step of reacting the active polymer with a compound represented by Formula 1 to prepare a modified conjugated diene-based polymer.

In this case, the compound represented by Chemical Formula 1 may be as described above.

The compound represented by Chemical Formula 1 may be used in a ratio of 0.01 mol to 10 mol with respect to the total number of moles of the organic alkali metal compound.

The reaction of step 2 according to an embodiment of the present invention is a modification reaction for introducing a functional group into the polymer, each reaction may be performed for 0 minutes to 5 hours in the temperature range of 0 ℃ to 90 ℃.

The preparation method according to an embodiment of the present invention may further include one or more steps of recovering and drying the solvent and the unreacted monomer, if necessary after step 2 above.

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

The rubber composition according to an embodiment of the present invention may be a modified conjugated diene-based polymer containing 10 wt% or more, specifically 10 wt% to 100 wt%, more specifically 20 wt% to 90 wt%. have. If the content of the modified conjugated diene-based polymer is less than 10% by weight, the effect of improving the wear resistance and crack resistance of a molded article, for example, a tire manufactured using the rubber composition may be insignificant.

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. Specifically, the modified conjugated diene copolymer may be included in an amount of 1 part by weight to 900 parts by weight based on 100 parts by weight.

The rubber component may be natural rubber or synthetic rubber, for example, the rubber component may 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.

In addition, the rubber composition may include 0.1 to 200 parts by weight of a filler with respect to 100 parts by weight of the modified conjugated diene-based polymer, the filler may be a silica-based filler, carbon black-based filler or a combination thereof.

Meanwhile, when the silica-based filler is used as the filler, a silane coupling agent may be used together to improve reinforcement and low heat generation.

Specific examples of the silane coupling agent include bis (3-triethoxysilylpropyl) tetrasulfide, bis (3-triethoxysilylpropyl) trisulfide, bis (3-triethoxysilylpropyl) disulfide, bis (2-triethoxysilylethyl) tetrasulfide, bis (3-trimethoxysilylpropyl) tetrasulfide, bis (2-trimethoxysilylethyl) tetrasulfide, 3-mercaptopropyltrimethoxysilane , 3-mercaptopropyltriethoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyltriethoxysilane, 3-trimethoxysilylpropyl-N, N-dimethylthiocarbamoyl tetrasul Feed, 3-triethoxysilylpropyl-N, N-dimethylthiocarbamoyl tetrasulfide, 2-triethoxysilylethyl-N, N-dimethylthiocarbamoyl tetrasulfide, 3-trimethoxysilyl Propylbenzothiazolyl tetrasulfide, 3-triethoxysilylpropylbenzolyl tetrasulfide, 3-triethoxysilylpropyl methacrylate Monosulfide, 3-trimethoxysilylpropylmethacrylate monosulfide, bis (3-diethoxymethylsilylpropyl) tetrasulfide, 3-mercaptopropyldimethoxymethylsilane, dimethoxymethylsilylpropyl-N, N-dimethylthiocarbamoyl tetrasulfide or dimethoxymethylsilylpropylbenzothiazolyl tetrasulfide, and the like, and any one or a mixture of two or more thereof may be used. More specifically, in consideration of the reinforcing improvement effect, the silane coupling agent may be bis (3-triethoxysilylpropyl) polysulfide or 3-trimethoxysilylpropylbenzothiazyl tetrasulfide.

In the rubber composition according to one embodiment of the present invention, a modified conjugated diene-based polymer having a functional group having high affinity with a silica-based filler as an active moiety is used as the rubber component. The compounding amount can be reduced than usual. Specifically, the silane coupling agent may be used in an amount of 1 to 20 parts by weight based on 100 parts by weight of the silica-based filler. When used in the above range, the gelation of the rubber component can be prevented while the effect as a coupling agent is sufficiently exhibited. More specifically, the silane coupling agent may be used in 5 parts by weight to 15 parts by weight based on 100 parts by weight of silica.

In addition, the rubber composition according to an embodiment of the present invention may be sulfur crosslinkable, and thus 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 based on 100 parts by weight of the rubber component. When included in the content range, it is possible to ensure the required elastic modulus and strength of the vulcanized rubber composition, and at the same time obtain a low fuel consumption.

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

The said vulcanization accelerator is not specifically limited, Specifically, M (2-mercapto benzothiazole), DM (dibenzothiazyl disulfide), CZ (N-cyclohexyl-2- benzothiazyl sulfenamide), etc. Thiazole compounds, or guanidine compounds such as DPG (diphenylguanidine) can be used. The vulcanization accelerator may be included in an amount of 0.1 parts by weight to 5 parts by weight based on 100 parts by weight of the rubber component.

In addition, the process oil acts as a softener in the rubber composition, specifically, may be a paraffinic, naphthenic, or aromatic compound, and more specifically, aromatic process oil, hysteresis loss in consideration of tensile strength and wear resistance. And naphthenic or paraffinic process oils may be used when considering low temperature properties. The process oil may be included in an amount of 100 parts by weight or less with respect to 100 parts by weight of the rubber component, when included in the content, it is possible to prevent the degradation of tensile strength, low heat generation (low fuel consumption) of the vulcanized rubber.

In addition, as the anti-aging agent, specifically N-isopropyl-N'-phenyl-p-phenylenediamine, N- (1,3-dimethylbutyl) -N'-phenyl-p-phenylenediamine, 6- Methoxy-2,2,4-trimethyl-1,2-dihydroquinoline, or a high temperature condensate of diphenylamine and acetone. The anti-aging agent may be used in an amount of 0.1 parts by weight 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 kneading machine such as a Banbury mixer, a roll, an internal mixer, etc. by the above formulation, and also 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.

Hereinafter, the present invention will be described in more detail with reference to Examples and Experimental Examples. However, the following Examples and Experimental Examples are provided to illustrate the present invention, and the scope of the present invention is not limited only to these examples.

The denaturing agent used in Examples 1 and 2 was used a compound represented by the following formula 2 according to an embodiment of the present invention.

[Formula 2]

Example 1

Into a 20 L autoclave reactor, 290 g of styrene, 780 g of 1,3 butadiene and 5500 g of normal hexane, 0.124 g of DTP (2,2-di (2-tetrahydrofuryl) propane) as a polar additive were added to the reactor. It heated up at 50 degreeC. When the internal temperature of the reactor reached 50 ° C, 4 mmol of n-butyllithium was added to the reactor to perform an adiabatic heating reaction. After 20 minutes, 20 g of 1,3-butadiene was added to cap the SSBR ends with butadiene. After 5 minutes, 0.181 g of denaturant was added and reacted for 15 minutes ([DTP] / [act.Li] = 2.3, [denaturant] / [act.Li] = 1.0). Thereafter, the polymerization was stopped using ethanol, and 45 ml of a solution in which 0.3 wt% of BHT (butylated hydroxytoluene), an antioxidant, was dissolved in hexane was added. The resulting polymer was placed in hot water heated with steam, stirred to remove the solvent, and then dried in rolls to remove residual solvent and water to prepare a modified styrene-butadiene copolymer.

Example 2

Into a 20 L autoclave reactor, 350 g of styrene, 600 g of 1,3 butadiene and 5500 g of normal hexane, 0.86 g of DTP (2,2-di (2-tetrahydrofuryl) propane) as a polar additive, It heated up at 50 degreeC. When the internal temperature of the reactor reached 50 ° C, 4 mmol of n-butyllithium was added to the reactor to perform an adiabatic heating reaction. After 20 minutes, 20 g of 1,3-butadiene was added to cap the SSBR ends with butadiene. After 5 minutes, 0.181 g of denaturant was added and reacted for 15 minutes ([DTP] / [act.Li] = 2.3, [denaturant] / [act.Li] = 1.0). Thereafter, the polymerization was stopped using ethanol, and 45 ml of a solution in which 0.3 wt% of BHT (butylated hydroxytoluene), an antioxidant, was dissolved in hexane was added. The resulting polymer was placed in hot water heated with steam, stirred to remove the solvent, and then dried in rolls to remove residual solvent and water to prepare a modified styrene-butadiene copolymer.

Comparative Example 1

A commercially available commercial styrene-butadiene copolymer (5025-2HM grade, LANXESS) was used for the experiment.

Comparative Example 2

A commercially available modified modified styrene-butadiene copolymer (TUFDENETM 3835, Asahi) was used for the experiment.

Experimental Example 1

The weight average molecular weight (Mw), the number average molecular weight (Mn), molecular weight distribution (MWD), component analysis and pattern viscosity (respectively) of the modified conjugated diene copolymers prepared in Examples 1, 2 and Comparative Examples, respectively. MV) was measured respectively. The results are shown in Table 1 below.

1) Component Analysis

Styrene derived units (SM) and vinyl content in each copolymer were measured using NMR.

2) Molecular Weight Analysis

The weight average molecular weight (Mw) and the number average molecular weight (Mn) of each copolymer were measured by gel permeation chromatograph (GPC) analysis under 40 ° C. At this time, the column (column) was used in combination with two bags of PLgel Olexis of Polymer Laboratories Co., Ltd. and one PLgel mixed-C column, all of the newly replaced column was a mixed bed column. In addition, PS (polystyrene) was used as the GPC standard material in the molecular weight calculation. The polydispersity index (PDI) was calculated as the ratio (Mw / Mn) of the weight average molecular weight and the number average molecular weight measured by the above method.

3) Mooney viscosity analysis

The Mooney viscosity of each copolymer was measured by MV-2000 (Alpha Technologies Co., Ltd.) for 15 minutes or more of each sample weight 15g or more for 1 minute and then at 100 ℃ for 4 minutes.

division Component Analysis (NMR) GPC Mooney viscosity (MV) Styrene vinyl Mw (g / mol, × 10 ³ ) Mn (g / mol, × 10 ³ ) Mp (g / mol, × 10 ³ ) MWD Example 1 27.0 43.1 448 320 245 1.4 88 Example 2 37.5 25.3 476 340 250 1.4 83 Comparative Example 1 26.0 50.0 690 390 - 1.8 61 Comparative Example 2 36.0 26.0 940 330 - 2.8 53

Experimental Example  2

In order to compare and analyze the physical properties of the rubber composition and the molded article prepared from each modified conjugated diene-based copolymer prepared in Examples 1, 2 and Comparative Examples, the tensile properties, vulcanization properties and viscoelastic properties were measured It was. The results are shown in Table 2 below.

1) Preparation of Rubber Composition

Each rubber composition was prepared through a first stage kneading process and a second stage kneading process. At this time, the amount of the substance except the modified conjugated diene copolymer is shown based on 100 parts by weight of the modified conjugated diene copolymer. In the first stage kneading, 137.5 parts by weight of each modified conjugated diene copolymer, 70 parts by weight of silica, and bis (3-triethoxysilylpropyl) tetrasulfate as a silane coupling agent using a half-variety mixer equipped with a temperature controller. 11.2 parts by weight of feed, 25 parts by weight of process oil (TDAE), 2 parts by weight of TMDQ, 3 parts by weight of zinc oxide (ZnO), 2 parts by weight of stearic acid, 1 part by weight of wax Kneaded. At this time, the temperature of the kneader was controlled and the primary blend was obtained at an outlet temperature of 150 ° C. In the second stage kneading, after cooling the primary blend to room temperature, 1.75 parts by weight of rubber accelerator (CZ), 1.5 parts by weight of sulfur powder, and 2 parts by weight of vulcanization accelerator are added to the kneader, followed by curing process for 150 to 20 minutes. A rubber composition was prepared. In this case, the silica had a nitrogen adsorption specific surface area of 175 m 2 / g and a CTAB adsorption of 160 m 2 / g.

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 specimen 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 measured by using a dynamic mechanical analyzer (TA Co., Ltd.) to determine the tan δ by changing the strain at a frequency of 10 Hz and measuring temperature (-60 ° C. to 60 ° C.) in a torsion mode. Payne effect is expressed as the difference between the minimum and maximum values at 0.28% to 40% strain. The higher the low temperature 0 [deg.] C tan δ, the better the wet road resistance. The lower the high temperature 60 [deg.] C tan δ, the lower the hysteresis loss, and the lower the cloud resistance (fuel efficiency).

division Example 1 Example 2 Comparative Example 1 Comparative Example 2 Tensile Properties Tensile strength (kgf / cm ² ) 203 194 161 177 300% tensile stress (kgf / cm ² ) 130 128 98 105 Viscoelastic Tan δ at 0 ° C (Index) 0.947 0.958 0.647 0.766 Tan δ at 60 ℃ (Index) 0.100 0.105 0.133 0.142 △ G 'at 60 ℃ 0.22 0.24 0.56 0.45

As shown in Table 2, the tensile properties and viscoelastic properties of the rubber composition comprising the modified styrene-butadiene copolymer of Example 1 and Example 2 prepared using a modifier according to an embodiment of the present invention And it was confirmed that compared to the rubber composition comprising a copolymer of Comparative Example 2.

Specifically, the styrene-butadiene copolymer of Comparative Example 1 in which the rubber composition comprising the modified styrene-butadiene copolymers of Examples 1 and 2 prepared by using the modifier according to an embodiment of the present invention is not modified It was confirmed that the Tan δ value at 0 ° C. and the Tan δ value at 60 ° C. were decreased compared to the rubber composition and commercially available modified styrene-butadiene copolymer of Comparative Example 2. This is a result showing that the modified styrene-butadiene copolymer prepared using the modifier according to the embodiment of the present invention has excellent resistance and rolling resistance on wet road surfaces, and high fuel efficiency.

In addition, the rubber composition comprising the modified styrene-butadiene copolymers of Examples 1 and 2 prepared using the modifier according to the embodiment of the present invention includes the styrene-butadiene copolymer of Comparative Example 1, which is not modified. It was confirmed that the ΔG ′ value was almost half lower than that of the modified styrene-butadiene copolymer of the rubber composition and the conventional Comparative Example 2. This is a result indicating that the rubber composition including the modified styrene-butadiene copolymer according to an embodiment of the present invention may have excellent silica dispersibility.

Claims (24)

Compound represented by the following formula (1):
[Formula 1]

In Chemical Formula 1,
R ₁ to R ₃ are each independently Alkyl having 1 to 20 carbon atoms,
A and B are independently alkylene having 1 to 20 carbon atoms.
The method according to claim 1,
In Chemical Formula 1,
R ₁ to R ₃ are each independently Alkyl having 1 to 10 carbon atoms,
A and B are independently from each other the alkylene having 1 to 10 carbon atoms.
The method according to claim 1,
In Chemical Formula 1,
R ₁ to R ₃ are each independently Alkyl having 1 to 6 carbon atoms,
A and B are independently of each other alkylene having 1 to 6 carbon atoms.
The method according to claim 1,
Formula 1 is a compound represented by the following formula (2):
[Formula 2]

The method according to claim 1,
The compound is a rubber modifier.
The method according to claim 1,
The compound is a modifier for conjugated diene polymer.
The method according to claim 6,
The conjugated diene-based polymer is a conjugated diene monomer homopolymer or a copolymer of a conjugated diene monomer and an aromatic vinyl monomer.
Modified conjugated diene-based polymer comprising a compound-derived functional group represented by the formula (1):
[Formula 1]

In Chemical Formula 1,
R ₁ to R ₃ are independently of each other Alkyl having 1 to 20 carbon atoms,
A and B are independently alkylene having 1 to 20 carbon atoms.
The method according to claim 8,
Wherein said polymer is a conjugated diene monomer homopolymer or a copolymer of a conjugated diene monomer and an aromatic vinyl monomer.
The method according to claim 8,
The polymer is a modified conjugated diene-based polymer having a number average molecular weight of 1,000 g / mol to 2,000,000 g / mol.
The method according to claim 8,
The polymer is a modified conjugated diene-based polymer having a polydispersity index of 0.5 to 10.
The method according to claim 8,
The polymer is modified conjugated diene-based polymer having a vinyl content of 5% by weight or more.
1) polymerizing a conjugated diene monomer or an aromatic vinyl monomer and a conjugated diene monomer in the presence of an organic alkali metal compound in a hydrocarbon solvent to prepare an active polymer having an alkali metal bonded to at least one end thereof; And
2) A method of preparing a modified conjugated diene-based polymer comprising the step of reacting the active polymer with a compound represented by the following formula (1):
[Formula 1]

In Chemical Formula 1,
R ₁ to R ₃ are each independently Alkyl having 1 to 20 carbon atoms,
A and B are independently of each other alkylene having 1 to 20 carbon atoms.
The method according to claim 13,
The organoalkali metal compound is a method for producing a modified conjugated diene-based polymer that is used in 0.01 mmol to 10 mmol based on a total of 100 g of the monomer.
The method according to claim 13,
The organoalkali metal compound is methyllithium, ethyllithium, propyllithium, n-butyllithium, s-butyllithium, t-butyllithium, hexyllithium, n-decyllithium, t-octylithium, phenyllithium, 1-naphthyl Lithium, n-eicosilium, 4-butylphenyllithium, 4-tolyllithium, cyclohexyllithium, 3,5-di-n-heptylcyclohexyllithium, 4-cyclopentyllithium, naphthyl sodium, naphthyl potassium, Of the modified conjugated diene-based polymer is one or more selected from the group consisting of lithium alkoxide, sodium alkoxide, potassium alkoxide, lithium sulfonate, sodium sulfonate, potassium sulfonate, lithium amide, sodium amide, potassium amide, lithium isopropylamide Manufacturing method.
The method according to claim 13,
The polymerization of step 1) is a method for producing a modified conjugated diene-based polymer further by adding a polar additive.
The method according to claim 16,
The polar additive is 0.001 to 50 parts by weight based on 100 parts by weight of the total monomer is a method for producing a modified conjugated diene polymer.
The method according to claim 13,
Formula 1 is a method for producing a modified conjugated diene-based polymer that is a compound represented by the formula (2):
[Formula 2]

The method according to claim 13,
The compound represented by Formula 1 is a method for producing a modified conjugated diene-based polymer that is used in a ratio of 0.01 mol to 10 mol relative to the number of moles of the organic alkali metal compound.

A rubber composition comprising the modified conjugated diene-based polymer of claim 8.
The method of claim 20,
The rubber composition is 0.1 to 100% by weight of a modified conjugated diene-based polymer.
The method of claim 20,
The rubber composition comprises 0.1 to 150 parts by weight of a filler with respect to 100 parts by weight of the polymer.
The method according to claim 22,
The filler is a silica-based filler, a carbon black filler or a combination thereof.
A tire made from the rubber composition of claim 20.