KR20170142491A - Modifying agent and modified conjugated diene polymer prepared by using the same - Google Patents

Abstract

Provided in the present invention are a modifying agent comprising an oximino-based compound of chemical formula 1, which can be easily modified by introducing an amino group which is a filler affinitive functional group, to rubber, in particular, a conjugated diene-based polymer; and a modified conjugated diene-based polymer prepared using the same. In the chemical formula 1, a-d, m, R^1, R^2, X, Y, and Z are the same as defined in the specification.

Description

MODIFIED AGENT AND MODIFIED CONJUGATED DIENE POLYMER PREPARED BY USING THE SAME [0002]

The present invention relates to a modifier and a modified conjugated diene polymer produced using the same.

In recent years, as a rubber material for a tire, a conjugated diene polymer having low rolling resistance, excellent abrasion resistance, tensile properties, and adjustment stability typified by a wet skid resistance has been required in recent years in response to demand for low fuel consumption in automobiles.

In order to reduce the rolling resistance of the tire, there is a method of reducing the hysteresis loss of the vulcanized rubber. As the evaluation index of such vulcanized rubber, repulsive elasticity of 50 DEG C to 80 DEG C, tan delta, Goodrich heat, and the like are used. That is, a rubber material having a large rebound resilience at that temperature or a small tan δ or Goodrich heating is preferable.

Natural rubbers, polyisoprene rubbers, polybutadiene rubbers, and the like are known as rubber materials having a small hysteresis loss, but these have a problem of low wet skid resistance. Recently, a conjugated diene (co) polymer such as styrene-butadiene rubber (hereinafter referred to as SBR) or butadiene rubber (hereinafter referred to as BR) is prepared by emulsion polymerization or solution polymerization and is used as a rubber for a tire . Of these, the greatest advantage of solution polymerization over emulsion polymerization is that vinyl structure content and styrene content, which define rubber properties, can be arbitrarily controlled and molecular weight and physical properties, etc., can be controlled by coupling, It can be adjusted. Therefore, it is easy to change the structure of the finally prepared SBR or BR rubber, and it is possible to reduce the movement of chain ends due to bonding or modification of chain ends and to increase the bonding force with a filler such as silica or carbon black, It is widely used as rubber material for tires.

When such a solution-polymerized SBR is used as a rubber material for a tire, the glass transition temperature of the rubber is increased by increasing the vinyl content in the SBR, so that the tire required properties such as running resistance and braking force can be controlled, Adjustment can reduce fuel consumption.

The solution-polymerized SBR is prepared by using an anionic polymerization initiator, and chain ends of the formed polymer are bonded or denatured by using various modifiers. For example, US Pat. No. 4,397,994 discloses a technique in which an active anion at the chain terminal of a polymer obtained by polymerizing styrene-butadiene in a nonpolar solvent using alkyllithium, a monofunctional initiator, is bonded using a binder such as a tin compound Respectively.

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

Generally, carbon black and silica are used as reinforcing fillers for tire treads. When silica is used as a reinforcing filler, hysteresis loss is small and wet skid resistance is improved. However, silica having a hydrophilic surface as compared to carbon black on the hydrophobic surface has a disadvantage that the affinity with the conjugated diene rubber is low and the dispersibility is poor, so that it is necessary to improve the dispersibility or to separate the silica- Of the silane coupling agent.

Thus, by introducing a functional group having affinity or reactivity with silica to the end of the rubber molecule, the silica dispersibility in the rubber composition is improved, and the mobility of the rubber molecule ends is reduced by bonding with the silica particles to reduce the hysteresis loss However, the effect is insufficient.

Therefore, it is necessary to develop a rubber having high affinity with a filler including silica.

US 4,397,994 A

SUMMARY OF THE INVENTION 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 modifier comprising an oxyimino compound.

Still another object of the present invention is to provide a modified conjugated diene polymer which is modified by the above modifier to contain a functional group derived from the oxyimino compound in the polymer, thereby exhibiting excellent affinity for the filler in the rubber composition.

Still another object of the present invention is to provide a rubber composition comprising the modified conjugated diene polymer and a tire produced therefrom with greatly improved rotational resistance characteristics.

According to one embodiment of the present invention, there is provided a modifier comprising an oxyimino compound represented by Formula 1:

[Chemical Formula 1]

In 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 an amino group substituted or unsubstituted with at least one functional group selected from the group consisting of a halogen group, an alkyl group having 1 to 6 carbon atoms and an alkoxy group having 1 to 6 carbon atoms, or a heterocyclic group containing at least one nitrogen atom ego,

Y represents 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 , 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 Or an unsubstituted, divalent hydrocarbon group of 1 to 20 carbon atoms,

Z is a functional group represented by the following formula (2)

(2)

In Formula 2,

R 'and R "each independently represents 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, 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 A monovalent hydrocarbon group of 1 to 20 carbon atoms which is unsubstituted or substituted with at least one functional group.

According to another embodiment of the present invention, there is provided a modified conjugated diene polymer comprising a functional group derived from an oxyimino compound represented by the general formula (1).

According to another embodiment of the present invention, there is provided a rubber composition comprising the modified conjugated diene polymer and a tire.

When applied as a modifier of a conjugated diene polymer, the oxyimino compound according to the present invention can provide an amino group having stronger affinity for a filler in a rubber composition such as silica or carbon black. Accordingly, the modified conjugated diene polymer having a functional group derived from the oxyimino compound can exhibit excellent affinity to a filler when applied to a rubber composition. As a result, it is possible to prevent aggregation of the filler in the rubber composition, So that the workability of the rubber composition can be improved. In addition, it is possible to improve the physical properties of the molded article produced using the rubber composition, and particularly to improve the rolling resistance characteristic of the tire, and to improve the fuel consumption characteristic, the wear characteristic and the braking characteristic with good balance.

Hereinafter, the present invention will be described in detail in order to facilitate understanding of the present invention.

The terms and words used in the present specification and claims should not be construed in an ordinary or dictionary sense and the inventor can properly define the concept of the term to describe its invention in the best possible way It should be construed as meaning and concept consistent with the technical idea of the present invention.

According to one embodiment of the present invention, there is provided a modifier comprising an oxyimino compound represented by the following formula (1), which can easily introduce and modify an amino group as a filler-affinity functional group to a rubber, particularly a conjugated diene polymer.

[Chemical Formula 1]

In 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 an amino group substituted or unsubstituted with at least one functional group selected from the group consisting of a halogen group, an alkyl group having 1 to 6 carbon atoms and an alkoxy group having 1 to 6 carbon atoms, or a heterocyclic group containing at least one nitrogen atom ego,

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

Z is a functional group represented by the following formula (2)

(2)

In Formula 2,

R 'and R "are each independently a monovalent hydrocarbon group of 1 to 20 carbon atoms, substituted or unsubstituted with at least one functional group defined below.

Specifically, in the above formula 1, R ¹ is a methoxy group, an alkoxy group having 1 to 6 carbon atoms such as an ethoxy group or propoxy group, more specifically, More specifically, methoxy group more than an alkoxy group, having 1 to 3 carbon atoms Or an ethoxy group.

In the above formula (1), R ² is a halogen group such as fluoro, chloro or bromo; Or an alkyl group having 1 to 6 carbon atoms such as a methyl group and an ethyl group. More specifically a halogen group or a straight 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 the above formula (1), X is an amino group substituted or unsubstituted with at least one functional group selected from the group consisting of a halogen group, an alkyl group having 1 to 6 carbon atoms and an alkoxy group having 1 to 6 carbon atoms, Or more. And when X is an amino group, it may be an amino group represented by the following formula (3):

(3)

-NR "" R"

In the above formula (3), R '' 'and R' '' 'each independently represent a monovalent hydrocarbon group having 1 to 6 carbon atoms, and more specifically, an alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 3 to 6 carbon atoms, And more specifically an alkyl group having 1 to 6 carbon atoms or 1 to 4 carbon atoms.

R "and R"" each independently represent a Halogen groups such as chloro, bromo and iodo; A straight chain 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 alkoxy groups having 1 to 6 carbon atoms or 1 to 3 carbon atoms such as methoxy, ethoxy, propoxy, n-butoxy and the like, and more specifically, methoxy And an ethoxy group may be substituted with one or more functional groups.

In the formula (1), when X is a heterocyclic group containing at least one nitrogen atom, specifically, X is a 5- to 8-membered heterocyclic group containing at least one nitrogen atom, more specifically 1 Membered to 5-membered to 6-membered heterocyclic group containing 1 to 3 nitrogen atoms. More specifically, X may be a piperidinyl group, a piperazinyl group, a methylpiperazinyl group, a pyrrolidinyl group, an imidazolinyl group, a pyrimidinyl group, A heterocycloalkyl group such as a pyrrolinyl group or a triazolinyl group or a heterocyclic group such as a pyridinyl group, a pyrazinyl group, a pyrimidinyl group, or a pyridazinyl group, ), Triazinyl, and the like, and X may be a piperazinyl group, a triazinyl group, or an imidazolinyl group.

The at least one hydrogen atom in the heterocyclic group may be substituted with a halogen group such as chloro, bromo or iodo; A straight chain 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 an alkoxy group having 1 to 6 carbon atoms or 1 to 3 carbon atoms such as methoxy, ethoxy, propoxy or n-butoxy group, and more specifically, And an ethoxy group may be substituted with one or more functional groups.

In formula (1), Y may be selected from the group consisting of specifically substituted or unsubstituted alkylene groups having 1 to 20 carbon atoms, arylene groups having 6 to 20 carbon atoms, and combinations thereof. (V) _p - (W) _q ] -, wherein V and W are each independently a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms or a substituted or unsubstituted alkylene group having 6 to 20 carbon atoms V and W are not mutually identical, and 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, more specifically, an alkylene group having 1 to 6 carbon atoms such as a methylene group, an ethylene group, or a propylene group, and particularly, a methylene group, an ethylene group Or a propylene group.

Y represents 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, an alkanoyloxy group having 2 to 12 carbon atoms (alkanoyl, R _a COO-, wherein R _a is an alkyl group having 1 to 9 carbon atoms), an aralkyloxy group having 7 to 13 carbon atoms, 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, a cycloalkyl group having 6 to 8 carbon atoms An aryl group having 7 to 10 carbon atoms, an arylalkyl group having 7 to 10 carbon atoms, and an alkylaryl group having 7 to 10 carbon atoms, and still more preferably 1 to 4 carbon atoms ≪ / RTI >

In formula (1), Z 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, 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 Alkyl group. More specifically, R 'and R "are each independently substituted or unsubstituted alkyl group having 1 to 6 carbon atoms Can.

Each of R 'and R' 'independently represents 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 aryloxy group having 6 to 12 carbon atoms, an alkanoyloxy group having 2 to 12 carbon atoms (alkanoyl, RaCOO-, wherein Ra is an alkyl group having 1 to 9 carbon atoms), an aralkyloxy group having 7 to 13 carbon atoms, An arylalkyl group having 1 to 13 carbon atoms, and an alkylaryl group having 7 to 13 carbon atoms, and more specifically may be substituted with any one or two or more substituents selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms , An aryl group having 6 to 8 carbon atoms, an arylalkyl group having 7 to 10 carbon atoms, and an alkylaryl 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 And more specifically may be substituted with an alkyl group having 1 to 4 carbon atoms.

More specifically, the oxyimino compound is represented by Formula 1, wherein m and a are each 1, b and c are each independently 1 or 2, d is 0, a + b + c + d = R ^{1 "} is an alkoxy group having 1 to 3 carbon atoms, X is an amino group of the above formula (3), R '" and R "" are each independently an unsubstituted alkyl group having 1 to 6 carbon atoms, and Y is an unsubstituted 1 to 6, and Z is a functional group of the above formula (2), wherein R 'and R "are each independently an unsubstituted alkyl group having 1 to 6 carbon atoms.

Specific examples thereof include compounds represented by the following general formula (1a) or (1b), and any one or a mixture of two or more thereof may be used.

[Formula 1a]

[Chemical Formula 1b]

More specifically, in the 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, Y is an unsubstituted C6- And Z is an alkyl group having 1 to 6 carbon atoms, which is a functional group of Formula 2 and R 'and R "are each independently an unsubstituted alkyl group.

Specific examples thereof include compounds represented by the following formula (1c) or (1d), and any one or a mixture of two or more thereof may be used.

[Chemical Formula 1c]

≪ RTI ID = 0.0 &

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

In the modifier according to an embodiment of the present invention, the oxyimino compound of Formula 1 is bonded to the activated terminal of the conjugated diene polymer, while the amino group bonded to the end of the conjugated diene polymer shows affinity for the filler such as silica, And the modified conjugated diene polymer can be promoted. As a result, it is possible to prevent the aggregation of the filler in the rubber composition and increase the dispersibility of the filler, thereby improving the workability of the rubber composition. In particular, it is possible to improve the fuel economy, wear and braking characteristics of the tire.

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

According to another embodiment of the present invention, there is provided a modified conjugated diene polymer modified by a modifier comprising an oxyimino compound represented by the above formula (1).

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

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.

When the modified conjugated diene-based polymer is a copolymer, the copolymer is a random copolymer having a structural unit derived from a conjugated diene-based monomer and a structural unit derived from an aromatic vinyl-based monomer, Lt; / RTI >

Specifically, the modified conjugated diene 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 polymer is more than 3.0 or less than 1.1, tensile properties and viscoelasticity may be deteriorated when applied to a rubber composition. The molecular weight distribution of the modified conjugated diene polymer may be specifically from 1.3 to 3.0 in view of the tensile property of the polymer and the remarkable effect of improving the viscoelasticity according to the molecular weight distribution control.

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

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

The modified conjugated diene polymer may have a number average molecular weight (Mn) of 50,000 g / mol to 2,000,000 g / mol, and more preferably 100,000 g / mol to 800,000 g / mol, / mol. < / RTI > The modified conjugated diene 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 modified conjugated diene polymer has a weight average molecular weight (Mw) of less than 100,000 g / mol / mol or a number average molecular weight (Mn) of less than 50,000 g / mol, there is a fear of deterioration of tensile properties when applied to a rubber composition. 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 the degradation of the workability of the modified conjugated diene polymer, The kneading of the kneaded mixture becomes difficult, and it may be difficult to sufficiently improve the physical properties of the rubber composition.

More specifically, when the modified conjugated diene polymer according to an embodiment of the present invention satisfies both the weight average molecular weight (Mw) and the number average molecular weight condition together with the molecular weight distribution described above, The tensile properties, the viscoelasticity and the workability can be improved and the balance can be improved.

The modified conjugated diene polymer may have a vinyl content of 5% by weight or more, specifically 30% by weight or more, more specifically 40% by weight to 50% by weight, based on the total weight of the polymer, The glass transition temperature can be adjusted to an appropriate range so that the physical properties required for a tire such as running resistance and braking force when applied to a tire can be improved.

Here, the vinyl content is not 1,4-added to the total weight of the conjugated diene-based polymer composed of the vinyl group-containing monomer or the conjugated diene-based monomer, and the content of the repeating unit of the 1,2-added conjugated diene- As a percentage.

Also, the modified conjugated diene 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. It is possible to exhibit better processability when having the Mooney viscosity in the above-mentioned range.

In the present invention, the Mooney viscosity can be measured using a Mooney viscometer, for example, Monsanto MV2000E at 100 占 폚 using Rotor Speed 2 占 0.02 rpm, Large Rotor. At this time, the used sample is allowed to stand at room temperature (23 ± 3 ° C) for more than 30 minutes, and 27 ± 3 g can be collected, filled in the die cavity, and measured by operating a platen.

According to another embodiment of the present invention, there is provided a method for producing the modified conjugated diene-based polymer using the modifier comprising the oxyimino compound of formula (1).

Specifically, the production method is characterized in that a conjugated diene monomer or an aromatic vinyl monomer and a conjugated diene monomer are polymerized in the presence of an organic alkali metal compound in a hydrocarbon solvent to form a conjugated diene-based monomer having an organic alkali metal moiety activated at least at one terminal thereof A step of preparing a polymer (step 1); And a step (step 2) of reacting the conjugated diene polymer with a modifier including an oxyimino compound of Formula 1 to prepare a modified conjugated diene polymer having at least one terminal end functional group-derived functional group bonded thereto.

The step (1) is a step for producing a conjugated diene polymer having at least one terminal organic alkali metal moiety, wherein the conjugated diene monomer in the presence of an organic alkali metal compound in a hydrocarbon solvent; Or by polymerizing an aromatic vinyl-based monomer and a conjugated diene-based monomer.

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

Examples of the conjugated diene monomer include, but are not limited to, 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, piperylene, 3-butyl-1,3-octadiene, -1,3-butadiene, and the like.

When the conjugated diene-based monomer and the aromatic vinyl-based monomer are used together as the monomer, the conjugated diene-based monomer has a unit derived from the conjugated diene-based monomer in the finally produced modified conjugated diene-based polymer in an amount of 60% by weight or more, In an amount of 60 wt% to 90 wt%, more specifically 60 wt% to 85 wt%.

Examples of the aromatic vinyl monomer include, but not limited to, styrene,? -Methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 1-vinylnaphthalene, 4-cyclohexylstyrene, 4- -Methylphenyl) styrene and 1-vinyl-5-hexyl naphthalene.

When the conjugated diene-based monomer and the aromatic vinyl-based monomer are used together as the monomer, the amount of the aromatic vinyl-based monomer-derived unit in the finally produced modified conjugated diene-based polymer is 40% by weight or less, , More preferably from 10% by weight to 40% by weight, and still more specifically from 15% by weight to 40% by weight.

The hydrocarbon solvent is not particularly limited, but may be 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 an amount of 0.1 to 1.0 mmol based on 100 g of the monomer for forming a conjugated diene-based polymer.

 The organic alkali metal compound is not particularly limited and includes, for example, methyl lithium, ethyl lithium, propyl lithium, n-butyl lithium, s-butyl lithium, t- Phenyl lithium, 1-naphthyl lithium, n-eicosyllithium, 4-butylphenyl lithium, 4-tolyl lithium, cyclohexyllithium, 3,5-di-n-heptylcyclohexyllithium, At least one member selected from the group consisting of lithium, sodium, potassium, sodium, potassium, sodium, sodium, potassium, sodium, sodium, potassium and alkaline earth metals. .

The polymerization of Step 1 may be carried out by adding a polar additive if necessary, and the polar additive may be added in an amount of 0.001 part by weight 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 in an amount of 0.005 part by weight to 0.5 part by weight, more specifically 0.01 part by weight to 0.3 part by weight, based on 100 parts by weight of the total amount of monomers.

The polar additive may be selected from the group consisting of tetrahydrofuran, ditetrahydrofuryl propane, diethyl ether, cycloalcohol ether, dipropyl ether, ethylenedimethyl ether, ethylene dimethyl ether, diethyl glycol, dimethyl ether, tertiary butoxyethoxyethane, bis (3-dimethylaminoethyl) ether, (dimethylaminoethyl) ethyl ether, trimethylamine, triethylamine, tripropylamine and tetramethylethylenediamine.

In the production 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 random copolymer can be easily formed .

The polymerization of the step 1 may be carried out through adiabatic polymerization or by isothermal polymerization.

Herein, the adiabatic polymerization represents a polymerization method comprising the step of polymerizing an organic alkali metal compound into a self-reaction heat without any heat, after the introduction of the organic alkali metal compound, wherein the isothermal polymerization is carried out by arbitrarily introducing heat Or the heat is taken to keep the temperature of the polymerizer constant.

The polymerization may be carried out in a temperature range of -20 캜 to 200 캜, specifically, in a temperature range of 0 캜 to 150 캜, more specifically, 10 캜 to 120 캜.

Step 2 is a denaturation step in which the active polymer is reacted with the aminosilane-based modifier of formula (1) to produce a modified conjugated diene polymer.

At this time, the aminosilane-based modifier of Formula 1 may be as described above. The aminosilane-based modifier of Formula 1 may be used in a proportion of 0.1 to 2.0 moles per mole of the organic alkali metal compound.

The reaction of Step 2 may be a modification reaction for introducing a functional group into the polymer, and each of the reactions may be carried out at a temperature ranging from 0 ° C to 90 ° C for 1 minute to 5 hours.

The manufacturing method according to an embodiment of the present invention may further include at least one step of recovering the solvent and unreacted monomers and drying as needed after the step 2.

According to another embodiment of the present invention, there is provided a rubber composition comprising the modified conjugated diene polymer.

By including the above-mentioned modified conjugated diene polymer, the rubber composition can improve the physical properties of the molded article, and particularly improve the fuel consumption characteristics, wear characteristics and braking characteristics of the tire in a well-balanced manner.

Specifically, the rubber composition may contain 0.1 to 100% by weight, specifically 10 to 100% by weight, more specifically 20 to 90% by weight, of the modified conjugated diene polymer. If the content of the modified conjugated diene polymer is less than 0.1% by weight, the effect of improving the fuel consumption characteristic, the wear characteristic and the braking characteristic in a molded article produced using the rubber composition, for example, a tire may be insignificant.

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

The rubber component may be natural rubber or synthetic rubber, for example natural rubber (NR) comprising cis-1,4-polyisoprene; Modified natural rubbers such as epoxidized natural rubber (ENR), deproteinized natural rubber (DPNR), and hydrogenated natural rubber, which are modified or refined with the general natural rubber; Butadiene copolymers (SBR), polybutadiene (BR), polyisoprenes (IR), butyl rubbers (IIR), ethylene-propylene copolymers, polyisobutylene-co-isoprene, neoprene, Butadiene), poly (styrene-co-butadiene), poly (styrene-co-butadiene) Synthetic rubber such as polysulfide rubber, acrylic rubber, urethane rubber, silicone rubber, epichlorohydrin rubber, butyl rubber, halogenated butyl rubber and the like may be used, and any one or a mixture of two or more thereof may be used have.

In addition, the rubber composition may contain 0.1 to 150 parts by weight of a filler based on 100 parts by weight of the modified conjugated diene polymer.

The filler may be specifically a silica filler or a carbon black filler, and either one or a mixture of the two may be used.

More specifically, the filler may be silica, and more specifically may be wet silica (hydrosilicic acid), dry silica (silicic anhydride), calcium silicate, aluminum silicate or colloidal silica, and the like. More specifically, the filler may be a wet silica having the most remarkable effect of improving the fracture characteristics and the wet grip.

On the other hand, when a silica-based filler is used as the filler, a silane coupling agent may be used together with the filler to improve the reinforcing property and the low heat build-up.

Specific examples of the silane coupling agent include bis (3-triethoxysilylpropyl) tetrasulfide, bis (3-triethoxysilylpropyl) trisulfide, bis (2-triethoxysilylethyl) tetrasulfide, bis (3-trimethoxysilylpropyl) tetrasulfide, bis (2-trimethoxysilylethyl) tetrasulfide, 3-mercaptopropyltrimethoxysilane , 3-mercaptopropyltriethoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyltriethoxysilane, 3-trimethoxysilylpropyl-N, N-dimethylthiocarbamoyltetrasulfide Triethoxysilylpropyl-N, N-dimethylthiocarbamoyltetrasulfide, 2-triethoxysilylethyl-N, N-dimethylthiocarbamoyltetrasulfide, 3-trimethoxysilyl Propylbenzothiazolyltetrasulfide, 3-triethoxysilylpropylbenzyltetrasulfide, 3-triethoxysilylpropylmethacrylate Monosulfide, monosulfide, 3-trimethoxysilylpropyl methacrylate monosulfide, bis (3-diethoxymethylsilylpropyl) tetrasulfide, 3-mercaptopropyldimethoxymethylsilane, dimethoxymethylsilylpropyl- N-dimethylthiocarbamoyltetrasulfide, or dimethoxymethylsilylpropylbenzothiazolyltetrasulfide. Any one or a mixture of two or more of them may be used. More specifically, in consideration of the reinforcing effect, the silane coupling agent may be bis (3-triethoxysilylpropyl) polysulfide or 3-trimethoxysilylpropylbenzothiazine tetrasulfide.

In the rubber composition according to the embodiment of the present invention, since the modified conjugated diene polymer having a functional group having a high affinity for the silica-based filler introduced into the active site is used as the rubber component, The compounding amount can be reduced more than usual. Specifically, the silane coupling agent may be used in an amount of 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-mentioned range, gelation of the rubber component can be prevented while sufficiently exhibiting the effect as a coupling agent. More specifically, the silane coupling agent may be used in an amount of 10 parts by weight 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 may further include a vulcanizing agent.

The vulcanizing agent may be specifically a 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 contained in the above content range, the required elastic modulus and strength of the vulcanized rubber composition can be ensured, and at the same time, the low fuel consumption ratio can be obtained.

In addition, the rubber composition according to one embodiment of the present invention may contain various additives commonly used in the rubber industry, such as a vulcanization accelerator, a process oil, a plasticizer, an antioxidant, a scorch inhibitor, zinc white ), Stearic acid, a thermosetting resin, or a thermoplastic resin.

The vulcanization accelerator is not particularly limited and specifically includes M (2-mercaptobenzothiazole), DM (dibenzothiazyl disulfide), CZ (N-cyclohexyl-2-benzothiazyl sulfenamide) Based compound, or a guanidine-based compound such as DPG (diphenylguanidine) can be used. The vulcanization accelerator may be included in an amount of 0.1 to 5 parts by weight based on 100 parts by weight of the rubber component.

The process oil may be a paraffinic, naphthenic, or aromatic compound. More specifically, considering the tensile strength and abrasion resistance, the process oil may be an aromatic process oil, a hysteresis loss And naphthenic or paraffinic process oils may be used in view of the low temperature characteristics. The process oil may be contained in an amount of 100 parts by weight or less based on 100 parts by weight of the rubber component. When the content is included in the above amount, the tensile strength and low heat build-up (low fuel consumption) of the vulcanized rubber can be prevented from lowering.

Specific examples of the antioxidant include N-isopropyl-N'-phenyl-p-phenylenediamine, N- (1,3-dimethylbutyl) -N'- 2, 4-trimethyl-1,2-dihydroquinoline, or high-temperature condensates of diphenylamine and acetone. The antioxidant may be used in an amount of 0.1 part by weight to 6 parts by weight based on 100 parts by weight of the rubber component.

The rubber composition according to one embodiment of the present invention can be obtained by kneading by using a kneader such as Banbury mixer, roll, internal mixer or the like by the above compounding formula. Further, the rubber composition can be obtained by a vulcanization step after molding, This excellent rubber composition can be obtained.

Accordingly, the rubber composition is applicable to various members such as tire tread, under tread, sidewall, carcass coating rubber, belt coating rubber, bead filler, or bead coating rubber, various industrial members such as vibration proof rubber, belt conveyor, May be useful in the manufacture of rubber products.

According to another embodiment of the present invention, there is provided a molded article and a tire produced using the rubber composition.

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 for illustrating the present invention, and the scope of the present invention is not limited thereto.

Example 1

270 g of styrene, 710 g of 1,3-butadiene and 5000 g of n-hexane were placed in a 20 L autoclave reactor, and 1.3 g of 2,2-bis (2-oxoranyl) propane was added as a polar additive. Lt; / RTI > When the internal temperature of the reactor reached 40 캜, 4 mmol of n-butyllithium was charged into the reactor to proceed the adiabatic temperature-rise reaction. After 20 minutes of reaction, 20 g of 1,3-butadiene was added to cap the end of the SSBR with butadiene. After 5 minutes, 4 mmol of the oxyimino compound represented by the following formula (1a) was added and reacted for 15 minutes. Thereafter, 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 resultant polymer was put into hot water heated with steam and stirred to remove the solvent. The solvent was then removed by roll drying to remove the remaining solvent and water to obtain a modified styrene-butadiene copolymer (yield: 99%).

(1a)

(1a)

Example 2

Butadiene copolymer was prepared in the same manner as in Example 1, except that 4 mmol of the oxyimino compound represented by the following formula (1c) was added in place of the oxyimino compound represented by the formula (1a) to carry out the modification reaction. (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 compound of Formula 1a was not performed.

Comparative Example 2

A modified styrene-butadiene copolymer was prepared in the same manner as in Example 1, except that 4 mmol of the compound of the formula (I) was added in place of the oxyimino compound of the formula (1a) to carry out the modification reaction.

(i)

(i)

Experimental Example 1

(Mw), number average molecular weight (Mn), polydispersion index (PDI), component analysis and pattern viscosity (MV) were measured for the polymers prepared in Examples 1 to 2 and Comparative Examples 1 and 2 Respectively. The results are shown in Table 1 below.

1) Component 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 GPC (gel permeation chromatograph) analysis under the condition of 40 占 폚. In this case, two columns of PLgel Olexis manufactured by Polymer Laboratories and a PLgel mixed-C column were used in combination, and all of the new columns were of mixed bed type. Also, PS (polystyrene) was used as a GPC reference material in molecular weight calculation. The polydispersity index (PDI) was calculated as the ratio (Mw / Mn) of the weight average molecular weight to the number average molecular weight measured by the above method.

3) Mooney viscosity analysis

The Mooney viscosity of each polymer was measured by MV-2000 (Alpha Technologies) at a temperature of 100 ° C for 4 minutes after preheating two samples each weighing 15 g or more for 1 minute.

Example 1 Example 2 Comparative Example 1 Amount of n-butyllithium (mmol) 4 4 4 Amount of denaturant (mmol) 4 4 4 Mooney viscosity (MV) 55 52 65 NMR Styrene content
(% By weight based on total polymer weight) 27.1 27.3 26.8 Vinyl content
(% By weight based on total polymer weight) 43.2 43.0 26.7 GPC Mn (x 10 < ⁴ > g / mol) 12.5 12.2 13.7 Mw (x 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 of the rubber compositions containing the modified styrene-butadiene copolymers of Examples 1 to 2 and Comparative Examples 1 and 2 and the molded articles produced from the rubber compositions were measured.

1) Preparation of rubber composition

Each rubber composition was manufactured through a first stage kneading, a second stage kneading and a third stage kneading. In this case, the amount of the material except for 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 was mixed with 80 parts by weight of bis (3-triethoxysilylpropyl) tetrasulfide as a silane coupling agent using a Banbury mixer equipped with a temperature controller, 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 were blended and kneaded. At this time, the temperature of the kneader was controlled and a primary blend was obtained at an outlet temperature of 140 ° C to 150 ° C. In the second stage kneading, after cooling the above-mentioned primary blend to room temperature, 1.75 parts by weight of a rubber accelerator (CZ), 1.5 parts by weight of sulfur powder and 2.0 parts by weight of a vulcanization accelerator were added to a kneader and mixed at a temperature of 60 DEG C or lower, ≪ / RTI > Thereafter, the second blend was molded in the third stage kneading and vulcanized by vulcanization press at 180 DEG C for t90 + 10 minutes to prepare each vulcanized rubber.

2) Tensile properties

Each test piece (thickness 25 mm, length 80 mm) was manufactured in accordance with the tensile test method of ASTM 412, and the tensile strength at the time of cutting the test piece and the tensile stress at 300% elongation (300% modulus) were measured. Specifically, tensile properties were measured at a rate of 50 cm / min at room temperature using a Universal Test Machin 4204 (Instron) tensile tester to obtain tensile strength and tensile stress values at 300% elongation.

3) Viscoelastic properties

The viscoelastic properties were measured by using a dynamic mechanical analyzer (TA) at a frequency of 10 Hz in a twist mode at various measuring temperatures (0 ° C to 60 ° C). The payne effect (ΔG ') is expressed as the difference between the minimum value and the maximum value at 0.28% to 40% of the strain, and the smaller the peening effect, the better the dispersibility of the filler. Also, the lower the tan 隆 at a high temperature of 60 캜, the lower the hysteresis loss and the lower the rolling resistance (fuel economy).

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 C 1.101 1.142 1.048 tanδ @ 60 ° C 0.079 0.080 0.089

As a result of the test, the rubber composition comprising the modified styrene-butadiene copolymer of Examples 1 and 2 modified by using the modifier according to the present invention was superior in both tensile strength, viscoelasticity and workability as compared with Comparative Example 1. [

Claims (13)

A modifier comprising an oxyimino compound represented by the following formula (1):
[Chemical Formula 1]

In 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 an amino group substituted or unsubstituted with at least one functional group selected from the group consisting of a halogen group, an alkyl group having 1 to 6 carbon atoms and an alkoxy group having 1 to 6 carbon atoms, or a heterocyclic group containing at least one nitrogen atom ego,
Y represents 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 , 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 Or an unsubstituted, divalent hydrocarbon group of 1 to 20 carbon atoms,
Z is a functional group represented by the following formula (2)
(2)

In Formula 2,
R 'and R "each independently represents 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, 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 A monovalent hydrocarbon group of 1 to 20 carbon atoms which is unsubstituted or substituted with at least one functional group.
The method according to claim 1,
X is an amino group of the following general formula (3), or is substituted with at least one functional group selected from the group consisting of a halogen group, a straight-chain or branched alkyl group having 1 to 6 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms Or an unsubstituted, 5- to 8-membered heterocyclic group containing 1 to 3 nitrogen atoms:
(3)
-NR ""R"
In the above formula (3), R '''andR''''each independently represent a substituent selected from the group consisting of a halogen group, a linear or branched alkyl group having 1 to 6 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms Or an unsubstituted or substituted alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 3 to 6 carbon atoms.
The method according to claim 1,
Wherein 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 a carbon number X is an amino group of the following general formula (3), Y is an unsubstituted alkylene group having 1 to 6 carbon atoms, Z is a functional group represented by the general formula (2), R 'and R " Substituted alkyl group having 1 to 6 carbon atoms.
(3)
-NR ""R"
In the above formula (3), R '''andR''''each independently represent an unsubstituted alkyl group having 1 to 6 carbon atoms.
The method according to claim 1,
Wherein 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, Y is an unsubstituted alkylene group having 1 to 6 carbon atoms , Z is a functional group of the above formula (2), and R 'and R "each independently represent an unsubstituted alkyl group having 1 to 6 carbon atoms.
The method according to claim 1,
Wherein the oxyimino compound comprises any one or a mixture of two or more compounds selected from the group consisting of compounds represented by the following formulas (1a) to (1d):
[Formula 1a]

[Chemical Formula 1b]

[Chemical Formula 1c]

≪ RTI ID = 0.0 &

A modified conjugated diene polymer comprising a functional group derived from an oxyimino compound represented by the following general formula:
[Chemical Formula 1]

In 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 an amino group substituted or unsubstituted with at least one functional group selected from the group consisting of a halogen group, an alkyl group having 1 to 6 carbon atoms and an alkoxy group having 1 to 6 carbon atoms, or a heterocyclic group containing at least one nitrogen atom ego,
Y represents 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 , 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 Or an unsubstituted, divalent hydrocarbon group of 1 to 20 carbon atoms,
Z is a functional group represented by the following formula (2)
(2)

In Formula 2,
R 'and R "each independently represents 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, 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 A monovalent hydrocarbon group of 1 to 20 carbon atoms which is unsubstituted or substituted with at least one functional group.
The method of claim 6,
Wherein the modified conjugated diene 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 of claim 6,
Wherein the number average molecular weight is from 50,000 g / mol to 2,000,000 g / mol, the weight average molecular weight is from 100,000 g / mol to 4,000,000 g / mol, and the molecular weight distribution is from 1.1 to 3.0.
The method of claim 6,
Wherein the vinyl content of the modified conjugated diene polymer is 30% by weight or more based on the total weight of the polymer.
A rubber composition comprising the modified conjugated diene polymer according to Claim 6.
The method of claim 10,
Wherein the rubber composition further comprises 0.1 to 150 parts by weight of a filler based on 100 parts by weight of the modified conjugated diene polymer.
The method of claim 11,
Wherein the filler is a silica-based filler.
A tire produced from the rubber composition according to claim 10.