KR102128570B1 - Modifying agent and modified conjugated diene polymer prepared by using the same - Google Patents

Abstract

상기 화학식 1에서, a~d, m, R¹, R², X, Y 및 Z는 명세서 중에서 정의한 바와 같다.In the present invention, a modified agent containing an oxyimino-based compound represented by the following Chemical Formula 1 and a modified conjugated diene-based product prepared by using an amino group, which is a filler-compatible functional group, can be easily modified with respect to rubber, in particular, a conjugated diene-based polymer Polymers are provided:
[Formula 1]

In Chemical Formula 1, a to d, m, R ¹ , R ² , X, Y and Z are as defined in the specification.

Description

Modifier and modified conjugated diene polymer prepared using the same {MODIFYING AGENT AND MODIFIED CONJUGATED DIENE POLYMER PREPARED BY USING THE SAME}

The present invention relates to a modified agent and a modified conjugated diene-based polymer prepared using the same.

Recently, in accordance with the demand for low fuel consumption for automobiles, a conjugated diene polymer having a low rolling resistance as a rubber material for tires, excellent abrasion resistance and tensile properties, and also having adjustment stability represented by wet skid resistance is required.

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

As the rubber material having low hysteresis loss, natural rubber, polyisoprene rubber, polybutadiene rubber and the like are known, but these have a problem of low wet skid resistance. Accordingly, recently, conjugated diene-based (co)polymers such as styrene-butadiene rubber (hereinafter referred to as SBR) or butadiene rubber (hereinafter referred to as BR) are manufactured by emulsion polymerization or solution polymerization and used as rubber for tires. . Among them, the greatest advantage of solution polymerization compared to emulsion polymerization is that the vinyl structure content and styrene content that regulate rubber properties can be arbitrarily controlled, and the molecular weight and physical properties can be adjusted by coupling, modification, etc. It is adjustable. Therefore, it is easy to change the structure of the final manufactured SBR or BR rubber, and it is possible to reduce the movement of the chain ends by bonding or denaturing the chain ends, and increase the bonding strength with fillers such as silica or carbon black. It is often used as a rubber material for tires.

When the solution-cured SBR is used as a rubber material for tires, it is possible to increase the glass content of the rubber by increasing the vinyl content in the SBR to adjust the required properties of tires such as driving resistance and braking force, as well as appropriately changing the glass transition temperature. By adjusting, fuel consumption can be reduced.

The solution polymerization SBR is prepared by using an anionic polymerization initiator, and the chain ends of the formed polymers are combined or modified by using various modifiers. For example, U.S. Patent No. 4,397,994 discloses a technique in which an active anion at the chain end of a polymer obtained by polymerizing styrene-butadiene in a non-polar solvent using a monofunctional initiator, alkyllithium, using a binder such as a tin compound Did.

On the other hand, as a material of a tire tread that comes into contact with the ground, there is a demand for a material having small rolling resistance, excellent wet grip and sufficient wear resistance in practical use.

In general, carbon black and silica are used as reinforcing fillers in tire treads, and when silica is used as reinforcing fillers, hysteresis loss is small and wet skid resistance is improved. However, the silica on the hydrophilic surface compared to the carbon black on the hydrophobic surface has a drawback that the dispersibility is poor due to low affinity with the conjugated diene-based rubber, so to improve dispersibility or to impart bonds between silica and rubber It is necessary to use a silane coupling agent.

Accordingly, by introducing a functional group having affinity or reactivity with silica at the end of the rubber molecule, the silica dispersibility in the rubber composition is improved, and the mobility of the end of the rubber molecule is reduced by bonding with the silica particles, thereby reducing hysteresis. Attempts have been made to reduce, but the effect is not sufficient.

Therefore, there is a need to develop rubbers having high affinity with fillers including silica.

US 4,397,994 A

The present invention has been devised to solve the problems of the prior art, and an object of the present invention is to provide a modifier comprising an oxyimino-based compound.

Another object of the present invention is to provide a modified conjugated diene-based polymer that exhibits excellent affinity for a filler in a rubber composition by being modified by the modifier to include functional groups derived from the oxyimino-based compound in the polymer.

In addition, another object of the present invention is to provide a rubber composition comprising the modified conjugated diene-based polymer and a tire having significantly improved rolling resistance characteristics.

In order to solve the above problems, according to an embodiment of the present invention provides a modifier comprising an oxyimino-based compound of Formula 1:

[Formula 1]

In Chemical Formula 1,

a, b and c are each independently 1 or 2, d is 0 or 1, a+b+c+d=4,

m is 0 or 1,

R ¹ is an alkoxy group having 1 to 6 carbon atoms,

R ² is a halogen group or an alkyl group having 1 to 6 carbon atoms,

X is a halogen group, an alkyl group having 1 to 6 carbon atoms and 1 or more functional groups selected from the group consisting of alkoxy groups having 1 to 6 carbon atoms, or an unsubstituted, amino group, or heterocyclic group containing one or more nitrogen atoms. ego,

Y is an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a cycloalkoxy group having 4 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aryloxy group having 6 to 12 carbon atoms , Substituted with one or more functional groups selected from the group consisting of alkanoyloxy groups having 2 to 12 carbon atoms, aralkyloxy groups having 7 to 13 carbon atoms, arylalkyl groups having 7 to 13 carbon atoms, and alkylaryl groups having 7 to 13 carbon atoms, or Or an unsubstituted, divalent hydrocarbon group having 1 to 20 carbon atoms,

Z is a functional group represented by the following formula 2,

[Formula 2]

In Chemical Formula 2,

R'and R" are each independently an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a cycloalkoxy group having 4 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, a carbon number Selected from the group consisting of an aryloxy group having 6 to 12 carbon atoms, an alkanoyloxy group having 2 to 12 carbon atoms, an aralkyloxy group having 7 to 13 carbon atoms, an arylalkyl group having 7 to 13 carbon atoms, and an alkylaryl group having 7 to 13 carbon atoms. It is a monovalent hydrocarbon group having 1 to 20 carbon atoms, which is unsubstituted or substituted with one or more functional groups.

In addition, according to another embodiment of the present invention provides a modified conjugated diene-based polymer comprising a functional group derived from the oxyimino-based compound of Formula 1 above.

In addition, according to another embodiment of the present invention, there is provided a rubber composition and a tire comprising the modified conjugated diene-based polymer.

When applied as a modifier of a conjugated diene-based polymer, the oxyimino-based compound according to the present invention can provide an amino group having a stronger affinity for a filler in a rubber composition such as silica or carbon black. Accordingly, the modified conjugated diene-based polymer having a functional group derived from the oxyimino-based compound can exhibit excellent affinity for the filler when applied to the rubber composition, and as a result, prevents agglomeration of the filler in the rubber composition and disperses the filler. It is possible to improve the processability of the rubber composition. In addition, the physical properties of the molded article manufactured using the rubber composition may be improved, and in particular, the rolling resistance characteristics of the tire may be greatly improved, and fuel efficiency, abrasion characteristics, and braking characteristics may be improved with good balance.

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

The terms or words used in the specification and claims should not be interpreted as being limited to ordinary or dictionary meanings, and the inventor can appropriately define the concept of terms in order to best describe his or her invention. Based on the principle of being present, it should be interpreted as meanings and concepts consistent with the technical spirit of the present invention.

According to an embodiment of the present invention provides a modifier comprising an oxyimino-based compound of Formula 1, which can be easily introduced and denatured with an amino group, which is a filler-affinity functional group, for rubber, particularly conjugated diene-based polymers.

[Formula 1]

In Chemical Formula 1,

a, b and c are each independently 1 or 2, d is 0 or 1, a+b+c+d=4,

m is 0 or 1,

R ¹ is an alkoxy group having 1 to 6 carbon atoms,

R ² is a halogen group or an alkyl group having 1 to 6 carbon atoms,

X is a halogen group, an alkyl group having 1 to 6 carbon atoms and 1 or more functional groups selected from the group consisting of alkoxy groups having 1 to 6 carbon atoms, or an unsubstituted, amino group, or heterocyclic group containing one or more nitrogen atoms. ego,

Y is a divalent hydrocarbon group having 1 to 20 carbon atoms which is unsubstituted or substituted with one or more functional groups as defined below,

Z is a functional group represented by the following formula 2,

[Formula 2]

In Chemical Formula 2,

R'and R" are each independently a monovalent hydrocarbon group having 1 to 20 carbon atoms, substituted or unsubstituted with one or more functional groups as defined below.

Specifically, in Chemical Formula 1, R ¹ is an alkoxy group having 1 to 6 carbon atoms, such as a methoxy group, an ethoxy group or a propoxy group, more specifically an alkoxy group having 1 to 3 carbon atoms, and more specifically a methoxy group Or it may be an ethoxy group.

Further, in Formula 1, R ² is a halogen group such as fluoro, chloro or bromo; Or it may be an alkyl group having 1 to 6 carbon atoms such as a methyl group and an ethyl group. More specifically, it may be a halogen group or a linear or branched alkyl group having 1 to 4 carbon atoms, and more specifically, it may be a chloro group, a methyl group, or an ethyl group.

In addition, in Formula 1, X is a halogen group, an alkyl group having 1 to 6 carbon atoms and 1 or more functional groups selected from the group consisting of an alkoxy group having 1 to 6 carbon atoms, or an unsubstituted, amino group or 1 nitrogen atom. It may be a heterocyclic group containing the above. Even when X is an amino group, it may be an amino group represented by the following formula (3):

[Formula 3]

-NR'"R""

In the formula (3), R'" and R"" may each independently be a monovalent hydrocarbon group having 1 to 6 carbon atoms, more specifically, an alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 3 to 6 carbon atoms, More specifically, it may be an alkyl group having 1 to 6 carbon atoms or 1 to 4 carbon atoms.

In addition, R'" and R"" are each independently Halogen groups such as chloro, bromo and iodo; A linear or branched alkyl group having 1 to 6 carbon atoms or 1 to 3 carbon atoms such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group or t-butyl group; And it may be substituted with one or more functional groups selected from the group consisting of alkoxy groups having 1 to 6 carbon atoms, or 1 to 3 carbon atoms, such as methoxy group, ethoxy group, propoxy group, n-butoxy group, and more specifically, methoxy It may be substituted with one or more functional groups selected from the group consisting of a group and an ethoxy group.

In addition, in Formula 1, when X is a heterocyclic group containing one or more nitrogen atoms, specifically X is a 5- to 8-membered heterocyclic group containing one or more nitrogen atoms, more specifically 1 It may be a 5 to 8 membered, or 5 to 6 membered heterocyclic group containing 3 to 3 nitrogen atoms. More specifically, X is a piperidinyl group, a piperazinyl group, a methylpiperazinyl group, a pyrrololidinyl group, an imidazolinyl group, a pi It is a heterocycloalkyl group such as a rollinyl group, a triazolinyl group, or a pyridinyl group, pyrazinyl group, pyrimidinyl group, or pyridazinyl group. ) Group, triazinyl (triazinyl), and the like, and may be a heteroaryl group, of which X may be a piperazinyl group, a triazinyl group, or an imidazolinyl group.

In addition, one or more hydrogen atoms in the heterocyclic group include halogen groups such as chloro, bromo, and iodo; A linear or branched alkyl group having 1 to 6 carbon atoms or 1 to 3 carbon atoms such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group or t-butyl group; And one or more functional groups selected from the group consisting of alkoxy groups having 1 to 6 carbon atoms or 1 to 3 carbon atoms, such as methoxy group, ethoxy group, propoxy group or n-butoxy group, and more specifically, It may be substituted with one or more functional groups selected from the group consisting of a group and an ethoxy group.

In addition, in Formula 1, Y may be specifically selected from the group consisting of substituted or unsubstituted alkylene groups having 1 to 20 carbon atoms, arylene groups having 6 to 20 carbon atoms, and combination groups thereof. When Y is a combination group, specifically -[(V) _p -(W) _q ]- (where V and W are each independently substituted or unsubstituted alkylene group having 1 to 20 carbon atoms or 6 to 20 carbon atoms. It may be an arylene group, V and W are not the same as each other, p and q are each independently an integer of 1 to 3). More specifically, Y may be an alkylene group having 1 to 10 carbon atoms, and more specifically, it may be an alkylene group having 1 to 6 carbon atoms, such as a methylene group, an ethylene group, or a propylene group. Or it may be a propylene group.

In addition, Y is an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a cycloalkoxy group having 4 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, or 6 to 12 carbon atoms. Aryloxy group, alkanoyloxy group having 2 to 12 carbon atoms (alkanoyl, R _a COO-, where R _a is an alkyl group having 1 to 9 carbon atoms), aralkyloxy group having 7 to 13 carbon atoms, aryl having 7 to 13 carbon atoms It may be substituted with one or more functional groups selected from the group consisting of an alkyl group and an alkylaryl group having 7 to 13 carbon atoms, and more specifically, an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, and 6 to 8 carbon atoms. It may be substituted with any one or more substituents selected from the group consisting of an aryl group, an arylalkyl group having 7 to 10 carbon atoms, and an alkylaryl group having 7 to 10 carbon atoms, and more specifically, substituted with an alkyl group having 1 to 4 carbon atoms. Can be.

In addition, Z in Formula 1 may be a functional group of Formula 2, wherein R'and R" in Formula 2 are each independently substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, and having 2 to 20 carbon atoms. It may be selected from the group consisting of an alkenyl group, an alkynyl group having 2 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, and an alkylaryl group having 7 to 20 carbon atoms. And more specifically, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkylaryl group having 7 to 12 carbon atoms, and an aryl group having 7 to 12 carbon atoms. It may be selected from the group consisting of alkyl groups, and more specifically, R'and R" may be independently substituted or unsubstituted alkyl groups having 1 to 6 carbon atoms.

In addition, R'and R" are each independently an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a cycloalkoxy group having 4 to 10 carbon atoms, and an aryl group having 6 to 12 carbon atoms. Group, an aryloxy group having 6 to 12 carbon atoms, an alkanoyloxy group having 2 to 12 carbon atoms (alkanoyl, RaCOO-, where Ra is an alkyl group having 1 to 9 carbon atoms), an aralkyloxy group having 7 to 13 carbon atoms, 7 carbon atoms It may be substituted with any one or two or more substituents selected from the group consisting of an arylalkyl group having 13 to 13, and an alkylaryl group having 7 to 13 carbon atoms, and more specifically, an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms. , Aryl group having 6 to 8 carbon atoms, arylalkyl group having 7 to 10 carbon atoms, and may be substituted with any one or two or more substituents selected from the group consisting of alkyl aryl groups having 7 to 10 carbon atoms, more specifically 1 carbon number To 4 alkyl groups.

More specifically, the oxyimino-based compound in Formula 1, m and a are each 1, b and c are each independently 1 or 2, d is 0, a+b+c+d=4, R ¹ is an alkoxy group having 1 to 3 carbon atoms, X is an amino group represented by Chemical Formula 3, wherein R'" and R"" are each independently an unsubstituted alkyl group having 1 to 6 carbon atoms, and Y is an unsubstituted carbon number. It may be a compound having 1 to 6 alkylene groups, and Z being a functional group of Formula 2, wherein R'and R" are each independently an unsubstituted alkyl group having 1 to 6 carbon atoms.

Specific examples thereof include compounds of Formula 1a or 1b below, and any one or a mixture of two or more of them may be used.

[Formula 1a]

[Formula 1b]

In addition, the oxyimino-based compound is more specifically, in Formula 1, m and a are each 1, b and c are each independently 1 or 2, d is 0, a+b+c+d=4, , R ¹ is an alkoxy group having 1 to 3 carbon atoms, X is a 5- to 6-membered heterocycloalkyl group containing 1 to 3 nitrogen atoms, or a heteroaryl group, and Y is unsubstituted 1 to 6 carbon atoms. It may be a alkylene group, Z is a functional group of the formula (2), R'and R" are each independently an unsubstituted alkyl group having 1 to 6 carbon atoms.

Specific examples thereof include compounds of Formula 1c or 1d below, and any one or a mixture of two or more of them may be used.

[Formula 1c]

[Formula 1d]

The oxyimino-based compound of Formula 1 having the above structure may be directly prepared using a known chemical reaction, or may be commercially obtained.

In the denaturing agent according to an embodiment of the present invention, the oxyimino-based compound of Formula 1 binds to the activated end of the conjugated diene-based polymer, while the amino group bound to the end shows affinity for a filler such as silica, and thus a filler. And a modified conjugated diene-based polymer. As a result, the agglomeration of the filler in the rubber composition can be prevented, and the dispersibility of the filler can be improved to improve the processability of the rubber composition, and in particular, the fuel efficiency, abrasion and braking characteristics of the tire can be improved with good balance.

The modifier according to an embodiment of the present invention may be a modifier for modifying the structure, properties, and properties of rubber, and may be a modifier of a conjugated diene-based polymer such as a butadiene-based polymer or a styrene-butadiene copolymer.

In addition, according to another embodiment of the present invention, a modified conjugated diene-based polymer modified by a modifier containing the oxyimino-based compound of Formula 1 is provided.

Specifically, the modified conjugated diene-based polymer may include a functional group derived from the oxyimino-based compound of Formula 1 above.

In addition, the conjugated diene-based polymer may be a homopolymer of a conjugated diene-based monomer or a copolymer of a conjugated diene-based monomer and an aromatic vinyl-based monomer.

In addition, when the modified conjugated diene-based polymer is a copolymer, the copolymer is a random copolymer in which the structural units constituting the copolymer, including the structural units derived from the conjugated diene-based monomers and the structural units derived from the aromatic vinyl-based monomers, are randomly arranged and bonded. May be

Specifically, the modified conjugated diene-based polymer may have a narrow molecular weight distribution (Mw/Mn) of 1.1 to 3.0. When the molecular weight distribution of the modified conjugated diene-based polymer is greater than 3.0 or less than 1.1, there is a fear that tensile properties and viscoelasticity are lowered when applied to a rubber composition. When considering the remarkable effect of improving the tensile properties and viscoelasticity of the polymer according to the molecular weight distribution control, the molecular weight distribution of the modified conjugated diene-based polymer may be specifically 1.3 to 3.0.

In the present invention, the molecular weight distribution of the modified butadiene-based polymer can be calculated from the ratio of weight average molecular weight (Mw) to number average molecular weight (Mn) (Mw/Mn). In this case, the number average molecular weight (Mn) is a common average of the individual polymer molecular weights calculated by dividing by n by measuring the molecular weight of n polymer molecules and calculating the sum of these molecular weights, and the weight average molecular weight (Mw) is the polymer. The molecular weight distribution of the composition is shown. All molecular weight averages can be expressed in grams per mole (g/mol).

In addition, in the present invention, the weight average molecular weight and the number average molecular weight are polystyrene converted molecular weights analyzed by gel permeation chromatography (GPC), respectively.

In addition, the modified conjugated diene-based polymer may satisfy the above molecular weight distribution conditions and have a number average molecular weight (Mn) of 50,000 g/mol to 2,000,000 g/mol, and more specifically 100,000 g/mol to 800,000 g. It may be /mol. In addition, the modified conjugated diene-based polymer may have a weight average molecular weight (Mw) of 100,000 g/mol to 4,000,000 g/mol, and more specifically 100,000 g/mol to 1,500,000 g/mol.

When the weight average molecular weight (Mw) of the modified conjugated diene-based polymer is less than 100,000 g/molg/mol or the number average molecular weight (Mn) is less than 50,000 g/mol, there is a fear of deterioration in tensile properties when applied to a rubber composition. In addition, when the weight average molecular weight (Mw) exceeds 4,000,000 g/mol or the number average molecular weight (Mn) exceeds 2,000,000 g/mol, the workability of the rubber composition deteriorates due to deterioration in processability of the modified conjugated diene-based polymer, Kneading is difficult, and it may be difficult to sufficiently improve the properties of the rubber composition.

More specifically, when the modified conjugated diene-based polymer according to an embodiment of the present invention simultaneously meets the weight average molecular weight (Mw) and number average molecular weight conditions together with the above-described molecular weight distribution, the rubber composition is applied to the rubber composition. It is possible to improve the balance without biasing the tensile properties, viscoelasticity, and workability.

In addition, the modified conjugated diene-based polymer may have a vinyl content of 5% by weight or more, specifically 30% by weight or more, and more specifically 40% to 50% by weight with respect to the total weight of the polymer. In the case of the range, the glass transition temperature can be adjusted to an appropriate range, and when applied to the tire, properties such as driving resistance and braking force can be improved.

In this case, the vinyl content is the content of the repeating unit of the structure derived from 1,2-added conjugated diene-based monomer rather than 1,4-added to the total weight of the conjugated diene-based polymer composed of a monomer having a vinyl group or a conjugated diene-based monomer. It is expressed as a percentage.

In addition, the modified conjugated diene-based polymer according to an embodiment of the present invention may have a Mooney viscosity (MV) at 100°C of 40 to 90, specifically 40 to 60. When it has the Mooney viscosity in the above range, it may exhibit better processability.

In the present invention, the Mooney viscosity can be measured using a Mooney viscosity meter, for example, a Rotor Speed 2±0.02 rpm, Large Rotor at 100°C with a MV2000E manufactured by Monsanto. At this time, the sample used can be measured by standing at room temperature (23±3℃) for 30 minutes or more, collecting 27±3g, filling it inside the die cavity, and operating the platen.

According to another embodiment of the present invention, a method for preparing the modified conjugated diene-based polymer using the modifier containing the oxyimino-based compound of Chemical Formula 1 is provided.

The manufacturing method is a conjugated diene system having an organic alkali metal moiety activated at least at one end by polymerizing a conjugated diene-based monomer or an aromatic vinyl-based monomer and a conjugated diene-based monomer in the presence of an organic alkali metal compound in a hydrocarbon solvent. Preparing a polymer (step 1); And reacting the conjugated diene-based polymer with a modifier containing the oxyimino-based compound of Formula 1 to prepare a modified conjugated diene-based polymer having a functional group derived from a modifier bonded to at least one terminal (step 2).

Step 1 is a step for preparing a conjugated diene-based polymer having an organic alkali metal moiety activated at least at one end thereof, a conjugated diene-based monomer in the presence of an organic alkali metal compound in a hydrocarbon solvent; Or it can be carried out by polymerizing an aromatic vinyl monomer and a conjugated diene monomer.

The polymerization of step 1 is a conjugated diene-based monomer alone as a monomer; Alternatively, the conjugated diene-based monomer and the aromatic vinyl-based monomer may be used together. That is, the polymer prepared through the above production method according to an embodiment of the present invention is a conjugated diene-based monomer homopolymer; Or it may be a copolymer derived from a conjugated diene-based monomer and an aromatic vinyl-based monomer.

The conjugated diene-based monomer is not particularly limited, 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-based monomer are used together as the monomer, the conjugated diene-based monomer has at least 60% by weight of a unit derived from the conjugated diene-based monomer in the finally prepared modified conjugated diene-based polymer, specifically It may be used in an amount included from 60% to 90% by weight, more specifically from 60% to 85% by weight.

The aromatic vinyl monomer is not particularly limited, such as styrene, α-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 1-vinylnaphthalene, 4-cyclohexylstyrene, 4-(p -Methylphenyl)styrene and 1-vinyl-5-hexylnaphthalene.

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

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 in 0.1mmol to 1.0mmol based on 100 g of the monomers for forming the conjugated diene polymer.

The organic alkali metal compound is not particularly limited, for example, methyl lithium, ethyl lithium, propyl lithium, n-butyl lithium, s-butyl lithium, t-butyl lithium, hexyl lithium, n-decyl lithium, t-octyl lithium, Phenyllithium, 1-naphthyllithium, n-eicosilium, 4-butylphenyllithium, 4-tolyllithium, cyclohexyllithium, 3,5-di-n-heptylcyclohexyllithium, 4-cyclopentyllithium, naphth One or more selected from the group consisting of sodium til sodium, naphthyl potassium, lithium alkoxide, sodium alkoxide, potassium alkoxide, lithium sulfonate, sodium sulfonate, potassium sulfonate, lithium amide, sodium amide, potassium amide and lithium isopropylamide Can.

The polymerization of step 1 may be performed by further adding a polar additive, if necessary, and the polar additive may be added in an amount of 0.001 part to 1.0 part by weight based on 100 parts by weight of the monomer for forming a conjugated diene polymer. . Specifically, it may be added to 0.005 parts by weight to 0.5 parts by weight, more specifically, 0.01 parts by weight to 0.3 parts by weight based on 100 parts by weight of the monomer.

The polar additives are 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.

The manufacturing method according to an embodiment of the present invention can be used to copolymerize the conjugated diene-based monomers and aromatic vinyl-based monomers by using the polar additives described above, thereby compensating for the difference in their reaction rates so that a random copolymer can be easily formed. Can be induced.

The polymerization of step 1 may be performed through adiabatic polymerization or isothermal polymerization.

Here, the adiabatic polymerization refers to a polymerization method including the step of polymerizing with the reaction heat itself without adding any heat after the organic alkali metal compound is added, and the isothermal polymerization randomly heats after the organic alkali metal compound is introduced. It shows a polymerization method that maintains the temperature of the polymer by adding or taking heat.

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

In step 2, a modified reaction step of reacting the active polymer with an aminosilane-based modifier of Formula 1 in order to prepare a modified conjugated diene-based polymer.

At this time, the aminosilane-based modifier of Chemical Formula 1 may be as described above. The aminosilane-based modifier of Chemical Formula 1 may be used in a ratio of 0.1 mol to 2.0 mol compared to 1 mol of the organic alkali metal compound.

The reaction of step 2 is a modification reaction for introducing a functional group into the polymer, and each reaction may be performed for 1 minute to 5 hours in a temperature range of 0°C to 90°C.

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

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

The rubber composition can improve the physical properties of the molded article by including the above-mentioned modified conjugated diene-based polymer, and in particular, it is possible to improve the fuel efficiency, abrasion characteristics and braking characteristics of the tire with good balance.

Specifically, the rubber composition may include 0.1% to 100% by weight of the modified conjugated diene polymer, specifically 10% to 100% by weight, and more specifically 20% to 90% by weight. If, if the content of the modified conjugated diene-based polymer is less than 0.1% by weight, as a result, a molded article manufactured using the rubber composition, for example, the improvement effect on fuel efficiency, wear characteristics and braking characteristics in tires may be negligible.

In addition, the rubber composition may further include other rubber components as necessary in addition to the modified conjugated diene-based polymer, wherein the rubber component may be included in an amount of 90% by weight or less based on the total weight of the rubber composition. Specifically, it may be included as 1 part by weight to 900 parts by weight based on 100 parts by weight of the modified conjugated diene-based copolymer.

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, which have been modified or purified from 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, synthetic rubber such as halogenated butyl rubber, etc., any one or a mixture of two or more of them can be used. have.

Further, the rubber composition may include 0.1 parts by weight to 150 parts by weight of a filler relative to 100 parts by weight of the modified conjugated diene-based polymer.

Specifically, the filler may be a silica-based filler or a carbon black-based filler, and a mixture of any one or two of them may be used.

More specifically, the filler may be silica, and more specifically, wet silica (hydrous silicic acid), dry silica (anhydrous silicic acid), calcium silicate, aluminum silicate, or colloidal silica. More specifically, the filler may be wet silica having the most remarkable effect of improving the breaking properties and the compatibility of wet grip.

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

Specifically, the silane coupling agent is 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-dimethylthiocarbamoyltetrasul Feed, 3-triethoxysilylpropyl-N,N-dimethylthiocarbamoyltetrasulfide, 2-triethoxysilylethyl-N,N-dimethylthiocarbamoyltetrasulfide, 3-trimethoxysilyl Propylbenzothiazolyltetrasulfide, 3-triethoxysilylpropylbenzolyltetrasulfide, 3-triethoxysilylpropylmethacrylate monosulfide, 3-trimethoxysilylpropylmethacrylate monosulfide, bis (3-diethoxymethylsilylpropyl)tetrasulfide, 3-mercaptopropyldimethoxymethylsilane, dimethoxymethylsilylpropyl-N,N-dimethylthiocarbamoyltetrasulfide or dimethoxymethylsilylpropylbenzothiazolyl Tetrasulfide and the like, and any one or a mixture of two or more of them may be used. More specifically, when considering the effect of improving the reinforcing properties, the silane coupling agent may be bis(3-triethoxysilylpropyl) polysulfide or 3-trimethoxysilylpropylbenzothiazyltetrasulfide.

In addition, in the rubber composition according to an embodiment of the present invention, since a modified conjugated diene-based polymer having a functional group having high affinity with a silica-based filler at an active site is used as a rubber component, a silane coupling agent is used. The blending amount can be reduced than usual. Specifically, the silane coupling agent may be used in 1 part by weight to 20 parts by weight based on 100 parts by weight of the silica-based filler. When used in the above range, it is possible to prevent the gelation of the rubber component while sufficiently exhibiting the effect as a coupling agent. More specifically, the silane coupling agent may be used in an amount of 10 to 20 parts by weight based on 100 parts by weight of the silica-based filler.

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 to 10 parts by weight based on 100 parts by weight of the rubber component. When included in the above content range, it is possible to secure the required elastic modulus and strength of the vulcanized rubber composition, and at the same time, low fuel efficiency can be obtained.

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

The vulcanization accelerator is not particularly limited, specifically M (2-mercaptobenzothiazole), DM (dibenzothiazyl disulfide), CZ (N-cyclohexyl-2-benzothiazylsulfenamide), etc. A thiazole-based compound, or a guanidine-based compound such as DPG (diphenylguanidine) can be used. The vulcanization accelerator may be included in 0.1 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 paraffin-based, naphthenic-based, or aromatic-based compound, and more specifically, considering the tensile strength and abrasion resistance, the aromatic-based process oil, hysteresis loss And when considering low-temperature properties, naphthenic or paraffinic process oils may be used. 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, and when included in the content, the tensile strength of the vulcanized rubber, low heat generation (low fuel consumption) can be prevented from falling.

In addition, specifically, the anti-aging agent is N-isopropyl-N'-phenyl-p-phenylenediamine, N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine, 6-e And high-temperature condensates of methoxy-2,2,4-trimethyl-1,2-dihydroquinoline or diphenylamine and acetone. The anti-aging agent may be used in an amount of 0.1 to 6 parts by weight based on 100 parts by weight of the rubber component.

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

Accordingly, the rubber composition is for tire tire, under tread, side wall, carcass coated rubber, belt coated rubber, bead filler, or bead coated rubber, for each member of tires, anti-vibration rubber, belt conveyor, hose, etc. It can be useful in the manufacture of rubber products.

In addition, according to another embodiment of the present invention, it provides a molded article and a tire manufactured using the rubber composition.

Hereinafter, the present invention will be described in more detail by examples and experimental examples. However, the following examples and experimental examples are intended to illustrate the present invention, but the scope of the present invention is not limited to them.

Example 1

In a 20 L autoclave reactor, 270 g of styrene, 710 g of 1,3-butadiene and 5000 g of normal hexane, and 1.3 g of 2,2-bis(2-oxolanyl)propane were added as polar additives, and the reactor internal temperature was 40°C. Was adjusted to. When the temperature inside the reactor reached 40°C, 4 mmol of n-butyllithium was introduced into the reactor to perform an adiabatic temperature increase reaction. After about 20 minutes of reaction, 20 g of 1,3-butadiene was added to cap the SSBR end with butadiene. After 5 minutes, 4 mmol of the oxyimino-based compound of Formula 1a was added and reacted for 15 minutes. Then, the polymerization reaction was stopped using ethanol, and 5 ml of a solution in which 0.3 wt% of BHT (butylated hydroxytoluene) as an antioxidant was dissolved in hexane was added. The resulting polymer was placed in hot water heated with steam and stirred to remove the solvent, and then roll dried to remove the residual amount of solvent and water to prepare a modified styrene-butadiene copolymer (yield: 99%).

(1a)

(1a)

Example 2

A modified styrene-butadiene copolymer was prepared in the same manner as in Example 1, except that the modification reaction was performed by adding 4 mmol of the oxyimino-based compound of Formula 1c instead of the oxyimino-based compound of Formula 1a. It was made (yield: 99%).

(1c)

(1c)

Comparative Example 1

Unmodified styrene-butadiene copolymer was prepared in the same manner as in Example 1, except that the modification reaction using the oxyimino-based compound of Formula 1a in Example 1 was not performed.

Comparative Example 2

A modified styrene-butadiene copolymer was prepared in the same manner as in Example 1, except that the modification reaction was carried out by adding 4 mmol of the compound of Formula i instead of the oxyimino-based compound of Formula 1a.

(i)

(i)

Experimental Example 1

For the polymers prepared in Examples 1 to 2, and Comparative Examples 1 to 2, the weight average molecular weight (Mw), number average molecular weight (Mn), polydispersity index (PDI), component analysis, and pattern viscosity (MV) were respectively determined. Each was measured. The results are shown in Table 1 below.

1) Ingredient analysis

The styrene-derived unit (SM) and vinyl content in each polymer were measured using NMR.

2) Molecular weight analysis

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

3) Mooney viscosity analysis

The Mooney viscosity of each polymer was measured by using MV-2000 (Alpha Technologies, Inc.), preheating two or more of each sample weight of 15 g for 1 minute, and then measuring at 100°C for 4 minutes.

Example 1 Example 2 Comparative Example 1 n-butyl lithium usage (mmol) 4 4 4 Modifier use (mmol) 4 4 4 Mooney viscosity (MV) 55 52 65 NMR Styrene content
(% by weight of the total polymer weight) 27.1 27.3 26.8 Vinyl content
(% by weight of the total polymer weight) 43.2 43.0 26.7 GPC Mn (×10 ⁴ g/mol) 12.5 12.2 13.7 Mw (×10 ⁴ g/mol) 13.6 13.5 14.8 PDI (Mw/Mn) 1.09 1.11 1.08

Experimental Example 2

Tensile properties and viscoelastic properties were measured in order to compare and analyze the properties of the rubber compositions each containing the modified styrene-butadiene copolymers of Examples 1 and 2 and Comparative Examples 1 and 2 and molded products prepared therefrom.

1) Preparation of rubber composition

Each rubber composition was prepared through a first-stage kneading, a second-stage kneading, and a third-stage kneading process. At this time, the amount of the material except the modified styrene-butadiene copolymer is shown based on 100 parts by weight of the modified styrene-butadiene copolymer. In the first stage kneading, 100 parts by weight of each of the above copolymers, 70 parts by weight of silica, and bis(3-triethoxysilylpropyl) tetrasulfone as a silane coupling agent using a vanari mixer attached to a temperature control device at 80 rpm. 11.11 parts by weight of feed, 33.75 parts by weight of process oil (TDAE), 2.0 parts by weight of antioxidant (TMDQ), 2.0 parts by weight of antioxidant, 3.0 parts by weight of zinc oxide (ZnO), 2.0 parts by weight of stearic acid and 1.0 part by weight of wax was blended and kneaded. At this time, the temperature of the kneader was controlled and the primary blend was obtained at a discharge temperature of 140°C to 150°C. In the second-stage kneading, after cooling the primary formulation to room temperature, a rubber promoter (CZ) of 1.75 parts by weight, 1.5 parts by weight of sulfur powder, and 2.0 parts by weight of a vulcanization accelerator are added and mixed at a temperature of 60°C or lower to mix the secondary mixture. Got Thereafter, the secondary blend was molded in the third-stage kneading, and vulcanized with vulcanizing press at 180°C for t90+10 minutes to prepare each vulcanized rubber.

2) Tensile properties

Tensile properties were prepared for each test piece (thickness 25 mm, length 80 mm) according to the tensile test method of ASTM 412, and the tensile strength at the time of cutting of the test piece and the tensile stress at 300% elongation (300% modulus) were measured. Specifically, the tensile properties were measured at a rate of 50 cm/min at room temperature using a Universal Test Machin 4204 (Instron Corporation) tensile tester to obtain tensile strength and tensile stress at 300% elongation.

3) Viscoelastic properties

The viscoelastic properties were measured by changing the strain at a frequency of 10 Hz and at each measurement temperature (0°C to 60°C) in a torsion mode using a dynamic mechanical analyzer (TA). The Payne effect (ΔG′) was expressed as the difference between the minimum value and the maximum value at 0.28% to 40% of the strain, and the smaller the Faye effect, the better the dispersibility of the filler. In addition, the lower the high temperature 60°C tan δ is, the less hysteresis loss is, and the lower the rolling resistance (fuel efficiency) is.

Example 1 Example 2 Comparative Example 1 300% modulus (Kgf/cm ² ) 158 159 148 Tensile strength (Kgf/cm ² ) 210 205 195 △G' 0.45 0.51 0.42 tanδ @ 0℃ 1.101 1.142 1.048 tanδ @ 60℃ 0.079 0.080 0.089

As a result of the experiment, the rubber compositions comprising the modified styrene-butadiene copolymers of Examples 1 and 2 modified with the modifier according to the present invention were superior in both tensile strength, viscoelasticity, and workability compared to Comparative Example 1.

Claims (13)

A modifier comprising an oxyimino-based compound of Formula 1:
[Formula 1]

In Chemical Formula 1,
m and a are each 1,
b and c are each independently 1 or 2,
d is 0, a+b+c+d=4,
R1 is 1 to 3 carbon atoms
An alkoxy group,
R2 is an alkyl group having 1 to 6 carbon atoms,
X is an amino group represented by the following formula (3),
Or contains 1 to 3 nitrogen atoms
5 to 6 membered heterocycloal
It's a killer,
Y is an unsubstituted alkylene group having 1 to 6 carbon atoms,
Z is a functional group represented by the following formula (2),
[Formula 2]

In Chemical Formula 2,
R'and R" are each independently an unsubstituted alkyl group having 1 to 6 carbon atoms,
[Formula 3]
-NR'"R""
In the above formula (3), R'" and R"" are each independently an unsubstituted alkyl group having 1 to 6 carbon atoms.
delete delete delete The method according to claim 1,
The oxyimino-based compound is a modifier comprising any one or two or more mixtures selected from the group consisting of compounds of Formulas 1a to 1d:
[Formula 1a]

[Formula 1b]

[Formula 1c]

[Formula 1d]

A modified conjugated diene-based polymer comprising a functional group derived from an oxyimino-based compound of Formula 1 below:
[Formula 1]

In Chemical Formula 1,
m and a are each 1,
b and c are each independently 1 or 2,
d is 0, a+b+c+d=4,
R1 is 1 to 3 carbon atoms
An alkoxy group,
R2 is an alkyl group having 1 to 6 carbon atoms,
X is an amino group represented by the following formula (3),
Or contains 1 to 3 nitrogen atoms
5 to 6 membered heterocycloal
It's a killer,
Y is an unsubstituted alkylene group having 1 to 6 carbon atoms,
Z is a functional group represented by the following formula (2),
[Formula 2]

In Chemical Formula 2,
R'and R" are each independently an unsubstituted alkyl group having 1 to 6 carbon atoms,
[Formula 3]
-NR'"R""
In the above formula (3), R'" and R"" are each independently an unsubstituted alkyl group having 1 to 6 carbon atoms.
The method according to claim 6,
The modified conjugated diene-based polymer is a modified polymer of a conjugated diene-based polymer selected from the group consisting of a homopolymer of a conjugated diene-based monomer or a copolymer of a conjugated diene-based monomer and an aromatic vinyl-based monomer.
The method according to claim 6,
A modified conjugated diene polymer having a number average molecular weight of 50,000 g/mol to 2,000,000 g/mol, a weight average molecular weight of 100,000 g/mol to 4,000,000 g/mol, and a molecular weight distribution of 1.1 to 3.0.
The method according to claim 6,
A modified conjugated diene polymer having a vinyl content of 30% by weight or more based on the total weight of the polymer.
A rubber composition comprising the modified conjugated diene-based polymer according to claim 6.
The method according to claim 10,
The rubber composition further comprises 0.1 parts by weight to 150 parts by weight of a filler relative to 100 parts by weight of the modified conjugated diene-based polymer.
The method according to claim 11,
The filler is a rubber composition that is a silica-based filler.
Tires made from the rubber composition according to claim 10.