KR102010458B1 - 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 modified conjugated diene-based polymer comprising a functional group derived from the compound, a method for producing a modified conjugated diene-based polymer using the compound, a rubber composition comprising the modified conjugated diene-based polymer and the rubber composition It is about an old tire. 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 by using the rubber modifier compound may have excellent affinity with the filler, and as a result, the processed product (eg, tire) manufactured from the rubber composition including the polymer may have tensile strength, Wear resistance, rolling resistance and wet road resistance properties can 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 modified conjugated diene-based polymer comprising a functional group derived from the compound, a method for producing a modified conjugated diene-based polymer using the compound, a rubber composition comprising the modified conjugated diene-based polymer and the rubber composition It is about an old tire.

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 bonding or modification of the chain ends, and the bonding strength with fillers such as silica or carbon black can be increased. 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.

On the other hand, carbon black and silica are used as reinforcing fillers for tire treads, and 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, and an object of the present invention is to provide a compound for a rubber modifier capable of providing 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 the compound-derived functional group.

Still another object of the present invention is to provide a method for preparing the modified conjugated diene polymer using the compound for rubber modifiers.

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, the present invention provides a triazole derivative compound containing at least four amine groups.

The present invention also provides a modified conjugated diene-based polymer comprising a functional group derived from the triazole derivative compound.

In addition, the present invention is to prepare an active polymer in which the alkali metal is bonded to at least one end 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 of reacting the active polymer with the triazole derivative compound (step 2).

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

The triazole derivative compound according to the present invention, specifically, the triazole derivative compound represented by the formula (1) or (2), is used as a modifier for rubber, in particular, a conjugated diene-based polymer, and is bonded to the conjugated diene-based polymer chain to form a filler. Affinity functional groups can be easily introduced.

In addition, the modified conjugated diene-based polymer according to the present invention has a functional group derived from a triazole derivative compound, specifically, a triazole derivative compound represented by the general formula (1) or (2), in a polymer chain, thereby making it possible to obtain Mars may be excellent.

In addition, the production method according to the present invention can easily prepare a modified conjugated diene polymer having excellent modification rate by using a triazole derivative compound as a modifier.

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 tensioned. Strength, wear resistance, low cloud 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 compounds for rubber modifiers which can provide affinity functional groups with reinforcing fillers, in particular silica-based fillers.

The compound according to an embodiment of the present invention may be a triazole derivative compound including at least four amine groups.

Here, the "at least four" refers to at least four, for example, may mean four or more.

Specifically, the triazole derivative compound according to an embodiment of the present invention is characterized by represented by the following formula (1) or formula (2).

[Formula 1]

[Formula 2]

In Chemical Formula 1 or Chemical Formula 2,

R ₁ to R ₃ are each independently an alkylene group having 1 to 18 carbon atoms,

R ₄ to R ₉ are each independently an alkyl group having 1 to 18 carbon atoms,

n is an integer from 0 to 10,

a, c and e are each independently an integer from 0 to 3.

Specifically, in Formula 1, R ₁ to R ₃ are each independently an alkylene group having 1 to 6 carbon atoms, R ₄ and R ₆ are independently an alkyl group having 1 to 4 carbon atoms, and R ₅ and R ₇ are mutually It may be independently an alkyl group having 1 to 10 carbon atoms.

In addition, in Formula 2, R ₁ to R ₃ are each independently an alkylene group having 1 to 6 carbon atoms, R ₄ , R ₆ and R ₈ are each independently an alkyl group having 1 to 4 carbon atoms, R ₅ , R ₇ and R ₉ is independently an alkyl group having 1 to 10 carbon atoms, and n may be an integer of 0 to 5, inclusive.

More specifically, Chemical Formula 1 may be represented by the following Chemical Formula 3.

[Formula 3]

In Formula 3, R ₄ and R ₆ are independently an alkyl group having 1 to 4 carbon atoms, and R ₅ and R ₇ are independently an alkyl group having 1 to 6 carbon atoms.

In addition, Chemical Formula 2 may be represented by the following Chemical Formula 4.

[Formula 4]

In Chemical Formula 4, R ₄ , R ₆ and R ₈ are each independently an alkyl group having 1 to 4 carbon atoms, and R ₅ , R ₇ and R ₉ are independently an alkyl group having 1 to 6 carbon atoms.

In addition, the triazole derivative compound may be a rubber modifier as described above.

Specifically, the triazole derivative compound may be a modifier for a silver 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.

The present invention also provides a modified conjugated diene-based polymer comprising a functional group derived from the triazole derivative compound.

The modified conjugated diene-based polymer according to an embodiment of the present invention is characterized in that represented by the formula (5) or formula (6).

[Formula 5]

[Formula 6]

In Chemical Formula 5 or Chemical Formula 6,

R ₁ to R ₃ are each independently an alkylene group having 1 to 18 carbon atoms,

R ₄ to R ₉ are each independently an alkyl group having 1 to 18 carbon atoms,

P is a conjugated diene polymer chain,

n is an integer from 0 to 10,

a, c and e are each independently an integer of 0 to 3,

b, d and f are each independently an integer of 1 to 3,

a + b, c + d and e + f are each independently an integer from 1 to 3.

Specifically, in Formula 5, R ₁ to R ₃ are independently an alkylene group having 1 to 6 carbon atoms, R ₄ and R ₆ are independently an alkyl group having 1 to 4 carbon atoms, and R ₅ and R ₇ are independent of each other It may be an alkyl group having 1 to 10 carbon atoms.

In addition, in Formula 6, R ₁ to R ₃ are each independently an alkylene group having 1 to 6 carbon atoms, R ₄ , R ₆ and R ₈ are each independently an alkyl group having 1 to 4 carbon atoms, and R ₅ , R ₇ and R ₉ is independently an alkyl group having 1 to 10 carbon atoms, and n may be an integer of 0 to 5, inclusive.

More specifically, Chemical Formula 5 may be represented by the following Chemical Formula 7.

[Formula 7]

In Formula 7, R ₄ and R ₆ are each independently an alkyl group having 1 to 4 carbon atoms, R ₅ and R ₇ are independently an alkyl group having 1 to 6 carbon atoms, P is a conjugated diene polymer chain, a and c Are independently of each other an integer of 0 to 2, b and d are independently of each other an integer of 1 to 3, a + b and c + d are independently of each other an integer of 1 to 3.

In addition, Chemical Formula 6 may be represented by the following Chemical Formula 8.

 [Formula 8]

In Formula 8 R ₄ , R ₆ And R ₈ is independently an alkyl group having 1 to 4 carbon atoms, R ₅ , R ₇ and R ₉ are each independently an alkyl group having 1 to 6 carbon atoms, P is a conjugated diene polymer chain, and a, c and e are each other Independently are integers from 0 to 2, b, d and f are independently integers from 1 to 3, and a + b, c + d and e + f are independently integers from 1 to 3;

The P may be a conjugated diene monomer homopolymer chain or a copolymer chain of a conjugated diene monomer and an aromatic vinyl monomer.

The modified conjugated diene-based polymer according to an embodiment of the present invention is a functional group derived from a triazole derivative compound in the polymer chain, specifically represented by the formula (1) or (2) in the polymer chain as shown in the formula (5) or (6) The compound-derived functional group may be bound.

Specifically, the modified conjugated diene-based polymer may include 0.001 mol% to 30 mol% of siloxane groups relative to the total moles of the polymer, and the polymer may include 0.001 mol% to 50 mol% of the amine groups relative to the total moles of the polymer. Can be.

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-based filler. Accordingly, the physical properties of the rubber composition including the modified conjugated diene-based polymer may be excellent, and as a result, a molded article manufactured using the rubber composition, for example, a tensile strength of a tire, 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 10,000 g / mol to 1,000,000 g / mol, specifically 30,000 g / mol to 700,000 g / mol.

The modified conjugated diene-based polymer may have a weight average molecular weight of 10,000 g / mol to 10,000,000 g / mol, specifically 30,000 g / mol to 7,000,000 g / mol.

The modified conjugated diene-based polymer may have a molecular weight distribution of 1 to 5, specifically 1 to 3.

In addition, the modified conjugated diene-based polymer may have a vinyl content of 3% by weight or more, specifically 5% 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 the modified conjugated diene-based polymer using the triazole derivative compound.

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 a triazole derivative compound (step 2).

Step 1 is a step for preparing an active polymer having an alkali metal bonded to at least one end thereof, and 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 organic alkali metal compound may be used according to the number average molecular weight of the active polymer to be prepared, specifically used in an amount such that the number average molecular weight of the active polymer is 10,000 g / mol to 1,000,000 g / mol It may be. For example, the organic alkali 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 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 10 parts by weight based on 100 parts by weight of the total monomer. Specifically, the amount may be added in an amount of 0.001 part by weight to 1 part by weight, and more specifically, 0.005 parts 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, tert-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 adiabatic polymerization, or isothermal polymerization.

Here, adiabatic polymerization refers to a polymerization method including a step of polymerizing with self-heating reaction without adding heat after the addition of the organoalkali metal compound, and the isothermal polymerization is an arbitrary heat after adding the organoalkali metal compound. It represents a polymerization method for maintaining a constant temperature of the polymer by adding or taking away heat.

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 and the triazole derivative compound to prepare a modified conjugated diene-based polymer.

Specific triazole derivative compounds may be as described above.

The triazole derivative compound may be used in a ratio of 0.01 mol to 10 mol relative 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 1 minute to 5 hours in the temperature range of 10 ℃ to 120 ℃.

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 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), solution polymerization styrene-butadiene copolymer (SSBR), 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., Any one or mixtures of two or more of these may be used.

In addition, the rubber composition according to an embodiment of the present invention may include 0.1 to 200 parts by weight of a filler based on 100 parts by weight of the modified conjugated diene-based polymer, the filler is a silica-based filler, carbon black filler Or a combination thereof.

On the other hand, when the silica-based filler is used as the filler, dispersibility is greatly improved, and the hysteresis loss is greatly reduced by bonding the silica particles of the filler with the modified conjugated diene-based polymer terminal. In addition, the rubber composition according to an embodiment of the present invention may be used with a silane coupling agent to improve the reinforcement and low heat generation when using a silica-based filler as a filler.

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 based on 100 parts by weight of the rubber component, for example, 10 parts by weight to 100 parts by weight, specifically 20 parts by weight to 80 parts by weight, based on 100 parts by weight of the conjugated diene polymer. May be included. If, when the process oil is included in the content, it is possible to prevent the degradation of the tensile strength, low heat generation (low fuel efficiency) 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.

Example 1

Four 10 L reactors equipped with a stirrer and a jacket were connected in series and dried in advance with nitrogen, followed by 318 g / hr of butadiene, 183 g / hr of styrene and 2500 g / hr of hexane, which had previously been freed of impurities. 0.95 g / hr of methyldetylenediamine) was charged to the first reactor. N-butyllithium was added to the reactor so as to be 1.082 g / hr. At this time, the temperature inside the reactor was maintained at 80 ℃. While passing through the second reactor was confirmed that 99% or more of butadiene and styrene was exhausted, 0.245 g / hr of the compound of formula (i) was added to the reactor and the reaction was performed at 80 ℃. At this time, the reaction was carried out in a third reactor. After the reaction, 2,6-di-t-butyl-p-cresol (BHT) was added at 5.0 g / hr to the reaction product from the third reactor, the solvent was removed by steam stiping, and dried to give a modified styrene- Butadiene copolymers were prepared.

(i)

(i)

Example 2

A modified styrene-butadiene copolymer was prepared in the same manner as in Example 1, except that the compound of formula (ii) was used instead of the compound of formula (i).

(ii)

(ii)

Comparative Example 1

A styrene-butadiene copolymer was prepared in the same manner as in Example 1 except that no modifier was used.

Comparative Example 2

A modified styrene-butadiene copolymer was prepared in the same manner as in Example 1 except that tetrachlorosilane was used instead of the compound of Formula (i).

Comparative Example 3

A modified styrene-butadiene copolymer was prepared in the same manner as in Example 1 except that tetraethyl orthosilicate (TEOS) was used instead of the compound of formula (i).

Experimental Example 1

The weight average molecular weight (Mw), number average molecular weight (Mn), molecular weight distribution (PDI), component analysis, and pattern viscosity (MV) for each of the copolymers of Examples 1 and 2 and Comparative Examples 1 to 3, respectively ) alc glass transition temperature (° C.) 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 molecular weight distribution (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.

4) Glass transition temperature

It was measured using DSC.

division Component Analysis (NMR) GPC Mooney viscosity (MV) Glass transition temperature
(℃) Styrene vinyl Mw (g / mol, X10 ⁴ ) Mn (g / mol, X10 ⁴ ) PDI Example 1 27.3 42.8 65 20 1.82 75 -25.0 Example 2 27.0 43.0 72 20 1.93 83 -24.9 Comparative Example 1 27.2 42.8 21 20 1.58 31 -24.7 Comparative Example 2 27.3 43.0 32 20 1.61 41 -24.5 Comparative Example 3 27.0 42.9 34 20 1.65 43 -24.8

Experimental Example 2

In order to compare and analyze the physical properties of the rubber composition and the molded article prepared from each of the copolymers of Examples 1 and 2 and Comparative Examples 1 to 3, the viscoelastic properties and wear resistance were measured. 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, using a half-barrier with a temperature control device, 100 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 8 parts by weight of feed, 37.5 parts by weight of process oil (TDAE), 2 parts by weight of antioxidant (TMDQ), 5 parts by weight of zinc oxide (ZnO), 5 parts by weight of stearic acid, 1 part by weight of wax and oxidation 2 parts by weight of the inhibitor (6PPD) was blended and kneaded. At this time, the temperature of the kneader was controlled and the primary blend was obtained at the discharge temperature of 145 ° C to 155 ° C. In the second stage kneading, after cooling the first blend to room temperature, 1.75 parts by weight of a rubber accelerator (CBS), 1.5 parts by weight of sulfur powder, and 2 parts by weight of vulcanization accelerator are added to the kneader, followed by mixing at a temperature of 100 ° C. or lower, and A blend was obtained. Each rubber composition was then prepared by a curing process for 100 to 20 minutes.

2) viscoelastic properties

The viscoelastic properties were measured by using a dynamic mechanical analyzer (TA, Inc.) in which the deformation was changed at a frequency of 10 Hz and each measurement temperature (-60 ° C. to 60 ° C.) in a torsion mode. The higher the low temperature 0 ° C Tan δ, the better the wet road surface resistance. The lower the high temperature 60 ° C Tan δ, the lower the hysteresis loss, and the lower the cloud resistance (fuel efficiency).

3) wear resistance

Abrasion resistance was crosslinked each rubber composition at 170 ℃ for 20 minutes using a crosslinked specimen manufacturing press to produce a test specimen, and then No. The volume reduction was measured by using the 152 Akron Type Tester (Yasuda Co., Ltd.) at the same time, 500 times of pre-wear and 3000 wear after 10 lb load at room temperature.

division Example 1 Example 2 Comparative Example 1 Comparative Example 2 Comparative Example 3 Viscoelastic Tan δ at 0 ° C (Index) 107 105 100 101 102 Tan δ at 60 ℃ (Index) 115 118 100 103 104 Wear Resistance (Index) 115 118 100 106 107

As shown in Table 2, the viscoelasticity and wear resistance of 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 It was confirmed that the rubber composition containing the copolymer of Comparative Example 2 is excellent.

Specifically, the styrene of Comparative Example 1 in which the rubber composition comprising the modified styrene-butadiene copolymers of Examples 1 and 2 prepared using the triazole derivative compound according to an embodiment of the present invention as a modifier is not modified. Tan δ value at 0 ° C. is increased compared to the rubber composition comprising butadiene copolymer and the rubber composition comprising the modified styrene-butadiene copolymer of Comparative Examples 2 and 3 modified using a conventional modifier (Index Numerical improvement), Tan δ at 60 ° C decreased (Index value improved), it was confirmed that the wear resistance increased (Index value improved). This result shows that the modified styrene-butadiene copolymer prepared by using the triazole derivative compound according to an embodiment of the present invention as a modifier may have excellent resistance and rolling resistance on wet roads and may have high fuel efficiency. In addition, it is also a result showing that the triazole derivative compound according to an embodiment of the present invention can be effectively used as a modifier of a rubber modifier, especially a conjugated diene polymer.

Claims (35)

Triazole derivative compound represented by the formula (2):
[Formula 2]

In Chemical Formula 2,
R ₁ to R ₃ are each independently an alkylene group having 1 to 6 carbon atoms,
R ₄ , R ₆ and R ₈ are each independently an alkyl group having 1 to 4 carbon atoms,
R ₅ , R ₇ and R ₉ are each independently an alkyl group having 1 to 10 carbon atoms,
n is an integer of 0 to 5, and a, c and e are integers of 0 to 3 independently of each other.
delete delete delete delete The method according to claim 1,
Formula 2 is a triazole derivative compound represented by the following formula (4):
[Formula 4]

In Chemical Formula 4,
R ₄ , R ₆ and R ₈ are each independently an alkyl group having 1 to 4 carbon atoms,
R ₅ , R ₇ and R ₉ are each independently an alkyl group having 1 to 6 carbon atoms.
The method according to claim 1,
The compound is a triazole derivative compound is a rubber modifier.
The method according to claim 1,
The compound is a triazole derivative compound that is a modifier for conjugated diene polymer.
The method according to claim 8,
The conjugated diene polymer is a triazole derivative compound which 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 functional group derived from the triazole derivative compound of claim 1.
The method according to claim 10,
The polymer is a modified conjugated diene-based polymer represented by the formula (6):
[Formula 6]

In Chemical Formula 6,
R ₁ to R ₃ are each independently an alkylene group having 1 to 6 carbon atoms,
R ₄ , R ₆ and R ₈ are each independently an alkyl group having 1 to 4 carbon atoms,
R ₅ , R ₇ and R ₉ are each independently an alkyl group having 1 to 10 carbon atoms,
P is a conjugated diene polymer chain,
n is an integer from 0 to 5,
a, c and e are each independently an integer of 0 to 3,
b, d and f are each independently an integer of 1 to 3,
a + b, c + d and e + f are each independently an integer from 1 to 3.
delete delete delete The method according to claim 11,
Formula 6 is a modified conjugated diene-based polymer represented by the following formula (8):
[Formula 8]

In Chemical Formula 8,
R ₄ , R ₆ and R ₈ is independently of each other an alkyl group having 1 to 4 carbon atoms,
R ₅ , R ₇ and R ₉ are each independently an alkyl group having 1 to 6 carbon atoms,
P is a conjugated diene polymer chain,
a, c and e are each independently an integer of 0 to 2,
b, d and f are each independently an integer of 1 to 3,
a + b, c + d and e + f are each independently an integer from 1 to 3.
The method according to claim 11,
Wherein P is a modified conjugated diene-based polymer is a conjugated diene monomer homopolymer chain or a copolymer chain of a conjugated diene monomer and an aromatic vinyl monomer.
The method according to claim 10,
The polymer is a modified conjugated diene-based polymer comprising 0.001 mol% to 30 mol% of siloxane groups relative to the total moles of the polymer.
The method according to claim 10,
The polymer is a modified conjugated diene-based polymer comprising 0.001 mol% to 50 mol% of the amine group based on the total moles of the polymer.
The method according to claim 10,
The polymer is a modified conjugated diene-based polymer having a number average molecular weight of 10,000 g / mol to 1,000,000 g / mol.
The method according to claim 10,
The polymer is a modified conjugated diene polymer having a molecular weight distribution of 1 to 5.
The method according to claim 10,
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 to prepare an active polymer having an alkali metal bonded to at least one end thereof in a hydrocarbon solvent; And
2) A method for preparing a modified conjugated diene-based polymer of claim 10 comprising the step of reacting the active polymer with a triazole derivative compound represented by the following formula (2):
[Formula 2]

In Chemical Formula 2,
R ₁ to R ₃ are each independently an alkylene group having 1 to 6 carbon atoms,
R ₄ , R ₆ and R ₈ are each independently an alkyl group having 1 to 4 carbon atoms,
R ₅ , R ₇ and R ₉ are each independently an alkyl group having 1 to 10 carbon atoms,
n is an integer of 0 to 5, and a, c and e are integers of 0 to 3 independently of each other.
delete The method according to claim 22,
The organic alkali metal compound is a method of producing a modified conjugated diene polymer that is used in an amount such that the number average molecular weight of the active polymer is 10,000 g / mol to 1,000,000 g / mol.
The method according to claim 22,
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 22,
The polymerization of step 1) is a method for producing a modified conjugated diene-based polymer further by adding a polar additive.
The method of claim 26,
The polar additive is a method for producing a modified conjugated diene-based polymer is added in an amount of 0.001 to 10 parts by weight based on 100 parts by weight of the total monomer.
delete The method according to claim 22,
Formula 2 is a method for producing a modified conjugated diene-based polymer represented by the following formula (4):
[Formula 4]

In Chemical Formula 4,
R ₄ , R ₆ and R ₈ are each independently an alkyl group having 1 to 4 carbon atoms,
R ₅ , R ₇ and R ₉ are each independently an alkyl group having 1 to 6 carbon atoms.
The method according to claim 22,
The triazole derivative compound 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 1 mol of the organic alkali metal compound.
A rubber composition comprising the modified conjugated diene-based polymer of claim 10.
The method according to claim 31,
The rubber composition is a rubber composition comprising 20 to 90% by weight of the modified conjugated diene-based polymer.
The method according to claim 31,
The rubber composition comprises 0.1 to 200 parts by weight of filler based on 100 parts by weight of polymer.
The method according to claim 33,
The filler is a rubber filler, a carbon black filler or a combination thereof.
A tire made from the rubber composition of claim 31.