KR20190066556A - Modified conjugated diene polymer and rubber composition comprising the same - Google Patents

Abstract

The present invention relates to a modified conjugated diene-based polymer. More specifically, the present invention relates to the modified conjugated diene-based polymer and a rubber composition comprising the same, wherein the modified conjugated diene-based polymer is manufactured by continuous polymerization, thereby having a specific polymer structure, a molecular weight distribution diagram, and a shape thereof. Therefore, it is possible to have excellent physical properties, since the modified conjugated diene-based polymer is excellent in processability and has a narrow molecular weight distribution.

Description

MODIFIED CONJUGATED DIENE POLYMER AND RUBBER COMPOSITION COMPRISING THE SAME [0002]

The present invention relates to a modified conjugated diene polymer excellent in workability and excellent in tensile properties and viscoelastic properties, and a rubber composition containing the modified conjugated diene polymer.

Recently, as a rubber material for a tire, there has been demanded a conjugated diene polymer having low rolling resistance, excellent abrasion resistance, tensile properties, and adjustment stability represented by wet road surface resistance, in accordance with recent 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 and 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 that wet road surface resistance is small. Recently, a conjugated diene polymer or copolymer such as styrene-butadiene rubber (hereinafter referred to as SBR) or butadiene rubber (hereinafter referred to as BR) has been produced 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, and it is possible to reduce the movement of the chain terminal due to bonding or modification of the chain terminal and increase the bonding force with the filler such as silica or carbon black, It is widely used as a rubber material.

When such a solution-polymerized SBR is used as a rubber material for a tire, by increasing the vinyl content in the SBR, it is possible to increase the glass transition temperature of the rubber to control tire properties such as running resistance and braking force, Proper control 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, U.S. Patent 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, the polymerization of SBR or BR can be carried out by batch or continuous polymerization. In the case of batch polymerization, the molecular weight distribution of the produced polymer is narrow, which is advantageous in terms of improvement in physical properties. However, , There is a problem that the processability is poor. In the case of the continuous polymerization, the polymerization is continuously performed, and the productivity is excellent, and the processability is improved, but the polymer has a wide molecular weight distribution and poor physical properties. Therefore, there is a continuing need for research to improve both productivity, processability and physical properties at the same time when manufacturing SBR or BR.

US 4397994 A JP 1994-271706 A

Disclosure of the Invention The present invention has been conceived to solve the problems of the prior art, and it is an object of the present invention to provide a modified conjugated diene polymer excellent in physical properties such as tensile properties and excellent in viscoelastic properties, And to provide a rubber composition.

According to one embodiment of the present invention, the molecular weight distribution curve by Gel Permeation Chromatography (GPC) has an unimodal form, and the molecular weight distribution (PDI; MWD) of not less than 1.0 and not more than 1.7, a functional group derived from a modifying agent represented by the following general formula (2) or (3) at one end and a functional group derived from a modifying initiator at one end, Wherein the modified conjugated diene-based polymer is a reaction product of a compound and an organometallic compound:

[Chemical Formula 1]

In Formula 1,

R ₁ to R ₅ independently from each other are hydrogen; An alkyl group having 1 to 30 carbon atoms; An alkenyl group having 2 to 30 carbon atoms; An alkynyl group having 2 to 30 carbon atoms; A heteroalkyl group having 1 to 30 carbon atoms, a heteroalkenyl group having 2 to 30 carbon atoms; A heteroalkynyl group having 2 to 30 carbon atoms; A cycloalkyl group having 5 to 30 carbon atoms; An aryl group having 5 to 30 carbon atoms; Or a heterocyclic group having 3 to 30 carbon atoms,

R ₆ is an alkyl group having 1 to 30 carbon atoms; An alkenyl group having 2 to 30 carbon atoms; An alkynyl group having 2 to 30 carbon atoms; A heteroalkyl group having 1 to 30 carbon atoms, a heteroalkenyl group having 2 to 30 carbon atoms; A heteroalkynyl group having 2 to 30 carbon atoms; A cycloalkyl group having 5 to 30 carbon atoms; An aryl group having 5 to 30 carbon atoms; Or an alkylene group having 1 to 20 carbon atoms which is substituted or unsubstituted with a heterocyclic group having 3 to 30 carbon atoms,

X is a functional group represented by the following formula (1a) or (1b)

[Formula 1a]

In formula (1a)

R ₇ and R ₈ are each independently an alkylene group of 1 to 20 carbon atoms, substituted or unsubstituted with an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or an aryl group having 5 to 20 carbon atoms,

R ₉ is hydrogen; An alkyl group having 1 to 30 carbon atoms; An alkenyl group having 2 to 30 carbon atoms; An alkynyl group having 2 to 30 carbon atoms; A heteroalkyl group having 1 to 30 carbon atoms; A heteroalkenyl group having 2 to 30 carbon atoms; A heteroalkynyl group having 2 to 30 carbon atoms; A cycloalkyl group having 5 to 30 carbon atoms; An aryl group having 5 to 30 carbon atoms; A heterocyclic group having 3 to 30 carbon atoms,

Y is N, O or S atom, and if Y is O or S, R ₉ is not present,

[Chemical Formula 1b]

In the above formula (1b)

R ₁₁ and R ₁₂ independently represent an alkyl group having 1 to 30 carbon atoms; An alkenyl group having 2 to 30 carbon atoms; An alkynyl group having 2 to 30 carbon atoms; A heteroalkyl group having 1 to 30 carbon atoms; A heteroalkenyl group having 2 to 30 carbon atoms; A heteroalkynyl group having 2 to 30 carbon atoms; A cycloalkyl group having 5 to 30 carbon atoms; An aryl group having 5 to 30 carbon atoms; A heterocyclic group having 3 to 30 carbon atoms,

(2)

In Formula 2,

R ₂₀ is a single bond or an alkylene group having 1 to 10 carbon atoms,

R ₂₁ and R ₂₂ are each independently an alkyl group having 1 to 10 carbon atoms or - [R ₄₂ O] _d -R ₄₃ ,

R ₂₃ is a single bond, an alkylene group having 1 to 10 carbon atoms, or - [R ₄₂ O] _d -

R ₂₄ is hydrogen or an alkyl group having 1 to 10 carbon atoms,

R ₄₂ is an alkylene group having 1 to 10 carbon atoms,

R ₄₃ is an alkyl group having 1 to 10 carbon atoms,

a is 2 or 3, c is an integer of 1 to 3, b is an integer of 0 to 2, b + c = 3, d is an integer of 1 to 30,

At least one of R ₂₁ to R ₂₃ necessarily includes the - [R ₄₂ O] _d - unit,

(3)

In Formula 3, Cy is a trivalent aromatic hydrocarbon group having 6 to 20 carbon atoms or a trivalent heteroaromatic hydrocarbon group having 3 to 20 carbon atoms,

R ₃₀ is a single bond, -NR ₄₄ -, -O-, -S-, or an alkylene group having 1 to 10 carbon atoms,

R ₃₁ and R ₃₂ are each independently an alkyl group having 1 to 10 carbon atoms,

R ₃₃ is - [R ₄₂ O] _d -

R ₃₄ is hydrogen or an alkyl group having 1 to 10 carbon atoms,

R ₄₂ is an alkylene group having 1 to 10 carbon atoms,

R ₄₄ is hydrogen or an alkyl group having 1 to 10 carbon atoms,

m is an integer of 0 to 3, k and n are integers of 1 or 2, k + n = 3, and d is an integer of 1 to 30.

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

The modified conjugated diene polymer according to the present invention is produced by continuous polymerization in which the polymerization conversion is controlled so that the molecular weight distribution curve by gel permeation chromatography has a unimodal shape and a molecular weight distribution is less than 1.7, Excellent in tensile and viscoelastic properties.

In addition, the modified conjugated diene polymer according to the present invention may further include a functional group derived from a modifying initiator at one end and a functional group derived from a modifier at another end.

BRIEF DESCRIPTION OF THE DRAWINGS The accompanying drawings, which are incorporated in and constitute a part of the specification, illustrate exemplary embodiments of the invention and, together with the description of the invention, It should not be construed as limited.
1 shows a molecular weight distribution curve of the modified conjugated diene polymer of Example 1 according to an embodiment of the present invention by gel permeation chromatography (GPC).
2 shows a molecular weight distribution curve of the modified conjugated diene polymer of Comparative Example 1 by gel permeation chromatography (GPC) according to an embodiment of the present invention.
3 shows the molecular weight distribution curve of the modified conjugated diene polymer of Reference Example 1 by gel permeation chromatography (GPC) according to an embodiment of the present invention.
4 shows the molecular weight distribution curve of the modified conjugated diene polymer of Reference Example 2 by Gel Permeation Chromatography (GPC) according to an embodiment of the present invention.

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 description of the present invention and in the claims should not be construed to be limited to ordinary or dictionary terms and the inventor should appropriately interpret the concept of the term appropriately The present invention should be construed in accordance with the meaning and concept consistent with the technical idea of the present invention.

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

In the present invention, the term 'alkylene group' may mean a bivalent aliphatic saturated hydrocarbon such as methylene, ethylene, propylene, and butylene.

The term " alkenyl group " in the present invention may mean an alkyl group containing one or more double bonds.

The term " alkynyl group " in the present invention may mean an alkyl group containing one or two or more triple bonds.

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

In the present invention, the term "aryl group" may mean a cyclic aromatic hydrocarbon, and may also refer to a monocyclic aromatic hydrocarbon having one ring formed, or a polycyclic aromatic hydrocarbon having two or more rings bonded thereto hydrocarbon < / RTI >

The term " heteroalkyl group " as used herein may mean an alkyl group in which the carbon atoms in the alkyl group (excluding the terminal carbon atoms) are substituted with one or more heteroatoms, wherein the heteroatoms are N, O and S ≪ / RTI >

The term " heteroalkenyl group " as used herein may mean an alkenyl group in which a carbon atom (except the terminal carbon atom) in the alkenyl group is substituted with one or more heteroatoms, wherein the heteroatom is N, O, and S, respectively.

The term " heteroalkynyl group " in the present invention may mean an alkynyl group in which a carbon atom (except the terminal carbon atom) in the alkynyl group is substituted with one or more hetero atoms, wherein the hetero atom is N, O, and S, respectively.

The term " heterocyclic group " in the present invention may be a cyclic saturated hydrocarbon, or a cycloalkyl group in which a carbon atom in a cyclic unsaturated hydrocarbon having at least one unsaturated bond is substituted with at least one heteroatom, N, < / RTI > O and S.

The term " derived unit " and " derived functional group " in the present invention may mean an ingredient, structure or the substance itself resulting from a substance.

The term " single bond " in the present invention may mean a single covalent bond itself not including a separate atom or a molecular end.

The present invention provides a modified conjugated diene polymer which is produced by continuous polymerization and has excellent processability and narrow molecular weight distribution and excellent physical properties.

The modified conjugated diene polymer according to an embodiment of the present invention has a molecular weight distribution curve by gel permeation chromatography (GPC) in an unimodal form and a molecular weight distribution (PDI; MWD) of 1.0 or more A modifier-derived functional group represented by the following general formula (2) or (3) at the other end, the modifying initiator comprising a compound represented by the following general formula (1) and an organometallic compound And the like.

[Chemical Formula 1]

In Formula 1, R ₁ to R ₅ independently represent hydrogen; An alkyl group having 1 to 30 carbon atoms; An alkenyl group having 2 to 30 carbon atoms; An alkynyl group having 2 to 30 carbon atoms; A heteroalkyl group having 1 to 30 carbon atoms, a heteroalkenyl group having 2 to 30 carbon atoms; A heteroalkynyl group having 2 to 30 carbon atoms; A cycloalkyl group having 5 to 30 carbon atoms; An aryl group having 5 to 30 carbon atoms; Or a heterocyclic group having 3 to 30 carbon atoms, R ₆ is an alkyl group having 1 to 30 carbon atoms; An alkenyl group having 2 to 30 carbon atoms; An alkynyl group having 2 to 30 carbon atoms; A heteroalkyl group having 1 to 30 carbon atoms, a heteroalkenyl group having 2 to 30 carbon atoms; A heteroalkynyl group having 2 to 30 carbon atoms; A cycloalkyl group having 5 to 30 carbon atoms; An aryl group having 5 to 30 carbon atoms; Or an alkylene group having 1 to 20 carbon atoms which is substituted or unsubstituted with a heterocyclic group having 3 to 30 carbon atoms, X is a functional group represented by the following general formula (1a) or (1b)

[Formula 1a]

In the formula (Ia), R ₇ and R ₈ independently represent an alkylene group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or an alkylene group having 1 to 20 carbon atoms substituted or unsubstituted with an aryl group having 5 to 20 carbon atoms , R ₉ is hydrogen; An alkyl group having 1 to 30 carbon atoms; An alkenyl group having 2 to 30 carbon atoms; An alkynyl group having 2 to 30 carbon atoms; A heteroalkyl group having 1 to 30 carbon atoms; A heteroalkenyl group having 2 to 30 carbon atoms; A heteroalkynyl group having 2 to 30 carbon atoms; A cycloalkyl group having 5 to 30 carbon atoms; An aryl group having 5 to 30 carbon atoms; A heterocyclic group having a carbon number of 3 to 30 and, Y is N, O or S atom, and if Y is O or S, R ₉ is not present,

[Chemical Formula 1b]

In the formula (1b), R ₁₁ and R ₁₂ independently represent an alkyl group having 1 to 30 carbon atoms; An alkenyl group having 2 to 30 carbon atoms; An alkynyl group having 2 to 30 carbon atoms; A heteroalkyl group having 1 to 30 carbon atoms; A heteroalkenyl group having 2 to 30 carbon atoms; A heteroalkynyl group having 2 to 30 carbon atoms; A cycloalkyl group having 5 to 30 carbon atoms; An aryl group having 5 to 30 carbon atoms; A heterocyclic group having 3 to 30 carbon atoms,

(2)

Wherein R ₂₀ is a single bond or an alkylene group having 1 to 10 carbon atoms, R ₂₁ and R ₂₂ are each independently an alkyl group having 1 to 10 carbon atoms or - [R ₄₂ O] _d -R ₄₃ , R ₂₃ is a single bond, an alkylene group having 1 to 10 carbon atoms, or - [R ₄₂ O] _d -, R ₂₄ is hydrogen, an alkyl group having 1 to 10 carbon atoms, R ₄₂ is an alkylene group having 1 to 10 carbon atoms, C is an integer of 1 to 3, b is an integer of 0 to 2, b + c = 3, and d is an integer of 1 to 30, wherein R < ₄₃ > is an alkyl group having 1 to 10 carbon atoms, a is 2 or 3, And at least one of R ₂₁ to R ₂₃ must contain - [R ₄₂ O] _d - units,

(3)

Cy is a trivalent aromatic hydrocarbon group having 6 to 20 carbon atoms or a trivalent heteroaromatic hydrocarbon group having 3 to 20 carbon atoms, and R ₃₀ is a single bond, -NR ₄₄ -, -O-, -S-, Or an alkylene group having 1 to 10 carbon atoms, R ₃₁ and R ₃₂ are independently an alkyl group having 1 to 10 carbon atoms, R ₃₃ is - [R ₄₂ O] _d -, and R ₃₄ is hydrogen, alkyl group, R ₄₂ is an alkylene group having 1 to 10, R ₄₄ is hydrogen or an alkyl group having 1 to 10, m is an integer from 0-3, an integer of k and n is 1 or 2, k + n = 3, and d is an integer of 1 to 30. [

According to one embodiment of the present invention, the modified conjugated diene polymer may include a repeating unit derived from a conjugated diene monomer, a functional group derived from a denaturation initiator, and a functional group derived from a denaturant. The repeating unit derived from the conjugated dienic monomer may mean a repeating unit formed by polymerization of the conjugated diene monomer, and the functional group derived from the modifying initiator and the functional group derived from the denaturing agent are each a modifying initiator derived from a modifying initiator or a modifier Functional group.

According to another embodiment of the present invention, the modified conjugated diene polymer may be a copolymer comprising a conjugated diene monomer-derived repeating unit, an aromatic vinyl monomer-derived repeating unit, a denaturation initiator-derived functional group and a denaturant-derived functional group . Here, the repeating unit derived from the aromatic vinyl monomer may mean a repeating unit formed by the aromatic vinyl monomer during polymerization.

According to an embodiment of the present invention, the conjugated diene-based monomer may be 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, -1,3-butadiene, and 2-halo-1,3-butadiene (wherein halo means a halogen atom).

Examples of the aromatic vinyl monomer include aromatic vinyl monomers such as styrene,? -Methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 1-vinylnaphthalene, 4-cyclohexylstyrene, 4- 2-pyrrolidino ethyl) styrene, 4- (2-pyrrolidinoethyl) styrene, 4- (2-pyrrolidinoethyl) styrene, ) styrene) and 3- (2-pyrrolidino-1-methylethyl) styrene) may be used.

As another example, the modified conjugated diene polymer may be a copolymer further comprising a repeating unit derived from a dienic monomer having 1 to 10 carbon atoms together with the repeating unit derived from the conjugated diene monomer. The diene-based monomer-derived repeating unit may be a repeating unit derived from a diene-based monomer different from the conjugated diene-based monomer, and the diene-based monomer different from the conjugated diene-based monomer may be 1,2-butadiene . When the modified conjugated diene polymer is a copolymer further comprising a diene monomer, the modified conjugated diene polymer may contain more than 0% by weight to 1% by weight, more than 0% by weight to 0.1% by weight, More than 0% by weight to 0.01% by weight, or more than 0% by weight to 0.001% by weight, and it is effective to prevent gel formation within this range.

According to one embodiment of the present invention, the copolymer may be a random copolymer, and in this case, there is an effect of excellent balance among physical properties. The random copolymer may mean that the repeating units constituting the copolymer are randomly arranged.

The modified conjugated diene polymer according to an embodiment of the present invention may have a number average molecular weight (Mn) of 1,000 g / mol to 2,000,000 g / mol, 10,000 g / mol to 1,000,000 g / mol, or 100,000 g / mol to 800,000 g / mol and may have a weight average molecular weight (Mw) of 1,000 g / mol to 3,000,000 g / mol, 10,000 g / mol to 2,000,000 g / mol, or 100,000 g / mol to 2,000,000 g / mol, (Mp) of from 1,000 g / mol to 3,000,000 g / mol, from 10,000 g / mol to 2,000,000 g / mol, or from 100,000 g / mol to 2,000,000 g / mol. Within this range, rolling resistance and wet road surface resistance are excellent.

As another example, the modified conjugated diene polymer preferably has a molecular weight distribution (PDI; MWD; Mw / Mn) of 2.5 or less and 2.3 or less, particularly preferably 1.7 or less, as a ratio of a weight average molecular weight (Mw) , Not less than 1.0 and not more than 1.7, or not less than 1.1 and not more than 1.7, and exhibits excellent tensile properties and viscoelastic properties within this range and excellent balance among physical properties.

At the same time, the modified conjugated diene polymer has a molecular weight distribution curve by gel permeation chromatography (GPC) having an unimodal shape, which is a molecular weight distribution in a polymer polymerized by continuous polymerization , It may mean that the modified conjugated diene polymer has uniform properties. That is, the modified conjugated diene polymer according to one embodiment of the present invention may be produced by continuous polymerization to have a molecular weight distribution curve of a unimodal form, and a molecular weight distribution of less than 1.7.

Generally, when the conjugated diene polymer is prepared by the batch polymerization method and the modification reaction is carried out, the molecular weight distribution curve of the produced modified conjugated diene polymer has a multimodal molecular weight distribution curve of bimodal or more. Specifically, in the case of the batch polymerization, the growth of each chain can be substantially uniform since the polymerization reaction is initiated after all of the raw materials are introduced and the chain growth can occur from the starting point generated by the plurality of initiators at the same time, It may be in the form of a unimodal with a narrow molecular weight distribution with a constant molecular weight of the polymer chains produced. However, when a denaturing agent is added to a denaturing reaction, there are two cases where the denaturation does not occur and the case where denaturation and coupling occur. Thus, the difference in molecular weight between the polymer chains is large Two groups may be formed, thereby forming a molecular weight distribution curve of a double bond having a peak of a molecular weight distribution curve of two or more. On the other hand, in the continuous polymerization method according to one embodiment of the present invention, unlike the batch polymerization, the start of the reaction and the introduction of the starting material are continuously performed, and the starting point at which the reaction is initiated is different, Polymer chains having various molecular weights can be produced when the polymerization reaction is completed, since initiation starts from the beginning of the reaction, starts in the middle of the reaction, and starts at the end of the reaction. As a result, a specific peak does not appear predominantly in the curve showing the distribution of the molecular weight, so that the molecular weight distribution curve is broad as a single peak. Even if the chain in which polymerization is initiated at the end of the reaction is coupled, the molecular weight of the chain And the distribution of the molecular weight distribution can remain the same.

However, even when a polymer is produced and modified by a batch polymerization method, the conditions for modification may be adjusted so as to have a unimodal form, but in this case, the entire polymer is not coupled or the entire polymer is coupled. , And in other cases, the molecular weight distribution curve of Unimodule can not be shown.

At this time, in the case of a polymer in which the whole is not coupled or the polymer is entirely coupled, there may arise a problem that the mooney relaxation rate of the polymer itself and the shrinkage factor are significantly lowered.

In addition, although the molecular weight distribution curve of the modified conjugated diene polymer shows a distribution of Unimodal, even when all of the polymers are coupled, only the polymers having the same level of molecular weight are present, May be poor and the functional properties capable of interacting with the filler such as silica or carbon black may be deteriorated due to the decrease in the coupling property, and in the opposite case, when all of the polymer is not coupled, A functional group at the end of the polymer which is to be interacted with a filler such as silica or carbon black may interfere with the interaction with the filler by interfacial interaction between the polymer terminal functional groups, , So that the polymer Prepared as if the control to have a molecular weight distribution curve of yunimo month and may have poor workability and physical properties of the formulation produced modified conjugated diene-based polymer problems, and in particular decrease the workability remarkably.

On the other hand, whether or not the modified conjugated diene polymer is coupled can be confirmed by the coupling number (CN), where the number of the functional groups after the denaturation of the polymer Dependent. That is, it is possible to have a range of 1 = CN < = F, which indicates the ratio of a polymer having only a terminal modification and no polymer chain coupling and a polymer having a plurality of polymer chains coupled to one modification agent, Refers to the number of functional groups capable of reacting with an active polymer end in a modifying agent. In other words, the modified conjugated diene polymer having the number of couplings of 1 means that all of the polymer chains are not coupled, and the modified conjugated diene polymer having the coupling number of F means that all the polymer chains are coupled.

Accordingly, the modified conjugated diene polymer according to an embodiment of the present invention may have a molecular weight distribution curve of Unimodal form, but the number of couplings is larger than 1 and smaller than the number of functional groups of the modifier used (1 <

As another example, the modified conjugated diene polymer may have a Si content of 50 ppm or more, 100 ppm or more, 100 ppm to 10,000 ppm, or 100 ppm to 5,000 ppm, based on the weight of the modified conjugated diene polymer, There is an effect of excellent mechanical properties such as tensile properties and viscoelastic characteristics of the rubber composition containing the polymer. The Si content may refer to the content of Si atoms present in the modified conjugated diene-based polymer. On the other hand, the Si atom may be derived from a modifier-derived functional group.

The Si content may be one measured by an ICP analysis method, and the ICP analysis method may be an ICP-OES (Optima 7300DV). When the inductively coupled plasma emission spectrometer was used, about 0.7 g of a sample was placed in a platinum crucible and about 1 mL of concentrated sulfuric acid (98% by weight, electronic grade) was added and heated at 300 캜 for 3 hours, Was conducted in an electric furnace (Thermo Scientific, Lindberg Blue M) with the program of the following steps 1 to 3,

1) initial temp 0 ° C, rate (temp / hr) 180 ° C / hr, temp (holdtime) 180 ° C (1hr)

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

3) step 3: initial temp 370 ° C, rate (temp / hr) 47 ° C / hr, temp (holdtime) 510 ° C

Add 1 mL of concentrated nitric acid (48% by weight) and 20 μL of concentrated hydrofluoric acid (50% by weight) to the residue. Seal the platinum crucible for 30 minutes or more and shake it. Then add 1 mL of boric acid , Stored at 0 ° C for 2 hours or more, diluted in ultrapure water (30 mL), and subjected to filtration. In addition, it is necessary that the sample is in a state in which the residual monomer and the residual denaturant are also removed in a state in which the solvent is removed by stirring in hot water heated with steam. When the oil is added, the oil is also removed through extraction and measured Lt; / RTI &gt;

As another example, the modified conjugated diene polymer may have an N content of 50 ppm or more, 100 ppm or more, 100 ppm to 10,000 ppm or 100 ppm to 5,000 ppm based on the total weight, and the modified conjugated diene polymer The rubber composition containing the polymer has excellent mechanical properties such as tensile properties and viscoelastic properties. The N content may refer to the content of N atoms present in the modified conjugated diene polymer, wherein the N atom may be derived from a modifier-derived functional group.

The N content may be one measured by an NSX analysis method, and the NSX analysis method may be measured by using a trace nitrogen analyzer (NSX-2100H). For example, when the Nitrogen Quantitative Analyzer is used, an autosampler (Horizontal furnace, PMT & Nitrogen detector) is turned on and 250 ml / min of Ar, 350 ml / min of O2, 300 ml / min of ozonizer , The heater was set at 800 DEG C, and the analyzer was stabilized by waiting for about 3 hours. After the analyzer was stabilized, calibration curves of 5 ppm, 10 ppm, 50 ppm, 100 ppm, and 500 ppm were prepared using the Nitrogen standard (AccuStandard S-22750-01-5 ml) A straight line was created using the ratio of posterior density to area. Then, a ceramic boat containing 20 mg of the sample was placed in an automatic sampler of the analyzer, and the area was measured. The N content was calculated using the area of the obtained sample and the calibration curve.

In this case, the sample used in the NSX analysis method may be a sample obtained by removing the residual monomer and the residual denaturant from the denatured conjugated diene polymer sample obtained by removing the solvent by stirring in hot water heated by steam. Further, if oil is added to the sample, it may be a sample after the oil is extracted (removed).

As another example, the modified conjugated diene polymer may have a Mooney moderation rate of 0.7 or more, 0.7 or more and 3.0 or less, 0.7 or more and 2.5 or less, or 0.7 or more and 2.0 or less, measured at 100 캜.

Here, the mooney relaxation rate represents a change in stress caused by a reaction with the same amount of strain, and may be measured using a Mooney viscometer. Specifically, the mooney relaxation rate was 27 ± 3 g after allowing the polymer to stand at room temperature (23 ± 5 ° C.) for 30 minutes or more at 100 ° C. and a rotor speed of 2 ± 0.02 rpm using a large rotor of Monsanto MV2000E And then filling the mold cavity into the die cavity. The platen was operated to measure the Mooney viscosity while applying a torque, and then measuring the slope of the Mooney viscosity change as the torque was released.

On the other hand, the mooney relaxation rate can be used as an index of the branch structure of the polymer. For example, when comparing polymers having the same Mooney viscosity, the mooney relaxation rate becomes smaller as the number of branches becomes larger.

The modified conjugated diene polymer may have a Mooney viscosity at 100 ° C of 30 or more, 40 to 150, or 40 to 140, and within this range, the modified conjugated diene polymer has excellent processability and productivity.

As another example, the modified conjugated diene polymer preferably has a shrinking factor (g ') of 0.8 or more, preferably 1.0 or more, more preferably 0.8 or more and 3.0 or less, as measured by gel permeation chromatography-light scattering method with a viscosity detector , More specifically 0.8 or more and 1.3 or less.

Here, the shrinkage factor g 'determined by the gel permeation chromatography-photolithographic method is the ratio of the intrinsic viscosity of the polymer having a branch to the intrinsic viscosity of a linear polymer having the same absolute molecular weight, Can be used as an index of the branch structure of the polymer, that is, the ratio of the branch, for example, as the shrinkage factor decreases, the branching index of the polymer tends to increase, The more branches are used, the smaller the shrinkage factor can be used as an indicator of branching.

The shrinkage factor was calculated based on the solution viscosity and the light scattering method by measuring the chromatogram using a gel chromatography-light scattering measurement apparatus equipped with a viscosity detector. Specifically, the shrinkage factor was measured using a column comprising a polystyrene- An absolute molecular weight and an intrinsic viscosity corresponding to each absolute molecular weight were obtained using a GPC-light scattering measurement apparatus equipped with a light scattering detector and a viscosity detector connected to each other, and the intrinsic viscosity of the linear polymer corresponding to the absolute molecular weight was calculated , And the shrinkage factor was determined as a ratio of intrinsic viscosity corresponding to each absolute molecular weight. Illustratively, the shrinkage factor was determined by measuring absolute molecular weight from a light scattering detector and measuring absolute molecular weight from a light scattering detector and a viscosity detector by injecting a sample into a GPC-light scattering measurement instrument (Viscotek TDAmax, Malvern) equipped with a light scattering detector and a viscosity detector The intrinsic viscosity [eta] of the linear polymer with respect to the absolute molecular weight is calculated to obtain the intrinsic viscosity [eta] / [ η] 0) is represented by the shrinkage factor. At this time, the eluent was prepared by mixing 20 mL of a mixed solution of N, N, N ', N'-tetramethylethylenediamine (N, N, N', N'- tetramethylethylenediamine, tetrahydrofuran and 1 L of tetrahydrofuran, ) Was used, and a column was PL Olexix (Agilent). The column was measured at an oven temperature of 40 ° C. and a THF flow rate of 1.0 mL / min. The sample was prepared by dissolving 15 mg of polymer in 10 mL of THF .

&Quot; (3) &quot;

^{_{[η] 0 = 10 -3.883 M}} 0.771

In the above formula (3), M is an absolute molecular weight.

The modified conjugated diene polymer may have a vinyl content of 5 wt% or more, 10 wt% or more, or 10 wt% to 60 wt%. Here, the vinyl content refers to the content of the 1,2-added conjugated diene monomer, not 1,4-added to 100% by weight of the conjugated diene-based copolymer composed of the monomer having vinyl group and the aromatic vinyl monomer .

Meanwhile, the modification initiator according to an embodiment of the present invention is produced by reacting a compound represented by the following general formula (1) with an organometallic compound, introducing a functional group at one end of a polymer chain It can be done.

[Chemical Formula 1]

In Formula 1, R ₁ to R ₅ independently represent hydrogen; An alkyl group having 1 to 30 carbon atoms; An alkenyl group having 2 to 30 carbon atoms; An alkynyl group having 2 to 30 carbon atoms; A heteroalkyl group having 1 to 30 carbon atoms, a heteroalkenyl group having 2 to 30 carbon atoms; A heteroalkynyl group having 2 to 30 carbon atoms; A cycloalkyl group having 5 to 30 carbon atoms; An aryl group having 5 to 30 carbon atoms; Or a heterocyclic group having 3 to 30 carbon atoms, R ₆ is an alkyl group having 1 to 30 carbon atoms; An alkenyl group having 2 to 30 carbon atoms; An alkynyl group having 2 to 30 carbon atoms; A heteroalkyl group having 1 to 30 carbon atoms, a heteroalkenyl group having 2 to 30 carbon atoms; A heteroalkynyl group having 2 to 30 carbon atoms; A cycloalkyl group having 5 to 30 carbon atoms; An aryl group having 5 to 30 carbon atoms; Or an alkylene group having 1 to 20 carbon atoms which is substituted or unsubstituted with a heterocyclic group having 3 to 30 carbon atoms, X is a functional group represented by the following general formula (1a) or (1b)

[Formula 1a]

In the formula (Ia), R ₇ and R ₈ independently represent an alkylene group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or an alkylene group having 1 to 20 carbon atoms substituted or unsubstituted with an aryl group having 5 to 20 carbon atoms , R ₉ is hydrogen; An alkyl group having 1 to 30 carbon atoms; An alkenyl group having 2 to 30 carbon atoms; An alkynyl group having 2 to 30 carbon atoms; A heteroalkyl group having 1 to 30 carbon atoms; A heteroalkenyl group having 2 to 30 carbon atoms; A heteroalkynyl group having 2 to 30 carbon atoms; A cycloalkyl group having 5 to 30 carbon atoms; An aryl group having 5 to 30 carbon atoms; A heterocyclic group having a carbon number of 3 to 30 and, Y is N, O or S atom, and if Y is O or S, R ₉ is not present,

[Chemical Formula 1b]

In the formula (1b), R ₁₁ and R ₁₂ independently represent an alkyl group having 1 to 30 carbon atoms; An alkenyl group having 2 to 30 carbon atoms; An alkynyl group having 2 to 30 carbon atoms; A heteroalkyl group having 1 to 30 carbon atoms; A heteroalkenyl group having 2 to 30 carbon atoms; A heteroalkynyl group having 2 to 30 carbon atoms; A cycloalkyl group having 5 to 30 carbon atoms; An aryl group having 5 to 30 carbon atoms; And a heterocyclic group having 3 to 30 carbon atoms.

Specifically, in the compound represented by Formula 1, R ₁ to R ₅ independently represent hydrogen; An alkyl group having 1 to 10 carbon atoms; An alkenyl group having 2 to 10 carbon atoms; Or an alkynyl group having 2 to 10, R ₆ is an alkylene group of 1 to 10 carbon atoms unsubstituted, X is a functional group represented by the formula 1a or formula 1b, in the formula 1a, R ₇ and R ₈ are each Independently, an unsubstituted alkylene group having 1 to 10 carbon atoms; R ₉ is an alkyl group having 1 to 10 carbon atoms; A cycloalkyl group having 5 to 20 carbon atoms; An aryl group having 5 to 20 carbon atoms; Or a heterocyclic group having 3 to 20 carbon atoms, Y is N, and in the above formula (1b), R ₁₁ and R ₁₂ independently represent an alkyl group having 1 to 10 carbon atoms; A cycloalkyl group having 5 to 20 carbon atoms; An aryl group having 5 to 20 carbon atoms; Or a heterocyclic group having 3 to 20 carbon atoms.

More specifically, the compound represented by Formula 1 may be a compound represented by Formula 1-1 or 1-2.

[Formula 1-1]

[Formula 1-2]

In addition, the organometallic compound may be an organic alkali metal compound and may be one or more selected from, for example, an organic lithium compound, an organosodium compound, an organic potassium compound, an organic rubidium compound, and an organic cesium compound.

Specifically, the organometallic compound is preferably selected from the group consisting of methyl lithium, ethyl lithium, isopropyl lithium, n-butyl lithium, sec-butyl lithium, tert- But may be one or more selected from lithium, n-eicolithium, 4-butylphenyllithium, 4-tolylithium, cyclohexyllithium, 3,5-di-n-heptylcyclohexyllithium and 4-cyclopentyllithium.

Further, the modifier according to the present invention may be a modifier for modifying the other end of the conjugated diene polymer, and may be a silica-affinity modifier, for example. The silica affinity modifier may be a modifier containing a silica affinity functional group in a compound used as a modifier, and the silica affinity functional group is excellent in affinity with a filler, particularly, a silica type filler, May refer to a functional group capable of interaction between the modifier-derived functional groups.

According to an embodiment of the present invention, the modifier may be a compound represented by the general formula (2), wherein R ₂₀ is a single bond or an alkylene group having 1 to 5 carbon atoms, R ₂₁ and R ₂₂ R ₄₂ O] _d -R ₄₃ , and R ₂₃ is a single bond, an alkylene group having 1 to 5 carbon atoms, or - [R ₄₂ O] _d -, and R ₂₄ Is an alkyl group having 1 to 5 carbon atoms, R ₄₂ is an alkylene group having 1 to 5 carbon atoms, R ₄₃ is an alkyl group having 1 to 5 carbon atoms, and d may be an integer of 1 to 10.

More specifically, the compound represented by Formula 2 may be N, N-bis (3- (triethoxysilyl) propyl) -2,5,8,11,14-pentaoxahexadecane-16- Bis (3- (diethoxymethylsilyl) propyl) -2,5,8,11,14-pentaoxahexadecan-16-amine), N, N, N-bis (3- (diethoxymethylsilyl) propyl) -2,5,8,11,14-pentaoxahexadecan-16-amine) Bis (3- (trimethoxysilyl) propyl) -3,6,9,12-tetraoxatetradecan-1 -amine (N, N-bis (3- 12-tetraoxateradecan-1-amine), N- (2,5,8,11,14-pentaoxahexadecan-16-yl) -N- (3- (triethoxysilyl) 8,11,14-pentaoxahexadecan-16-amine (N- (2,5,8,11,14-pentaoxahexadecan-16-yl) -N- (3- (triethoxysilyl) propyl) 8,11,14-pentaoxahexadecan-16-amine) and N- (3,6,9,12-tetraoxahexadecyl) -N- (3- (triethoxysilyl) Tetraoxahexadecan-1 -amine (N- (3,6,9,12-tetraoxahexadecyl) -N- (3- (triethoxysilyl) propyl) -3,6,9,12-tetraoxahexadecan-1-amine).

According to another embodiment of the present invention, the modifier may be a compound represented by the general formula (3), wherein Cy preferably represents a benzene ring, a pyridine ring, a pyrimidine ring or a triazine ring R ₃₀ is -NR ₄₄ - or an alkylene group having 1 to 5 carbon atoms, R ₃₁ and R ₃₂ are each independently an alkyl group having 1 to 5 carbon atoms, R ₃₄ is an alkyl group having 1 to 5 carbon atoms, R ₄₂ is an alkylene group having 1 to 5 carbon atoms, R ₄₄ is hydrogen, an alkyl group having 1 to 3 carbon atoms, and d may be an integer of 1 to 10.

(3-triethoxysilyl) propyl) aniline (3,4-bis (2-methoxyethoxy) (2-methoxyethoxy) -N-methyl-N- (3- (triethoxysilyl) propyl) aniline, 3,4- Aniline, 3,4-bis (2-methoxyethoxy) -N- (3- (triethoxysilyl) propyl) aniline, N, (2-methoxyethoxy) ethyl-3- (triethoxysilyl) propan-1-amine) and 2,4-bis (2-methoxyethoxy) (2,4-bis (2-methoxyethoxy) -6 - ((triethoxylsilyl) methyl) -1,3,5-triazine) And the like.

As described above, in the modified conjugated diene polymer according to one embodiment of the present invention, the polymer has a specific structure and may have a specific molecular weight distribution diagram and shape. The structure of such a polymer can be expressed by physical properties such as shrinkage factor, mooni relaxation rate, coupling number, and the molecular weight distribution diagram and its form can be expressed by the PDI value and the shape of the molecular weight distribution curve and coupling number, And metamorphosis with metamorphic initiators can affect structure and molecular weight distributions and their morphology. The parameters expressing the structure of such a polymer and the characteristics related to the molecular weight distribution can be satisfied according to the production method described later, and although it is preferable for the preparation through such a production method to satisfy the above-mentioned characteristics, If all are satisfied, the effect to be implemented in the present invention can be achieved.

The present invention also provides a process for producing the modified conjugated diene polymer.

In the method for producing a modified conjugated diene-based polymer according to an embodiment of the present invention, the conjugated diene-based monomer or the conjugated diene-based monomer and the aromatic vinyl monomer are polymerized in a hydrocarbon solvent in the presence of a modifying initiator, Preparing a polymer (S1); And (S2) reacting or coupling the active polymer prepared in the step (S1) with a modifier represented by the following formula (2) or (3), wherein the step (S1) And the polymerization conversion in the first reactor of the polymerization reactor is 50% or less. The modification initiator may be a reaction product prepared by reacting a compound represented by the following formula (1) with a free metal compound.

[Chemical Formula 1]

(2)

(3)

In the above Chemical Formulas 1 to 3, the respective substituents and indices are as defined above.

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 conjugated diene monomer and the aromatic vinyl monomer are as defined above.

According to one embodiment of the present invention, the modification initiator is used in an amount of 0.01 mmol to 10 mmol, 0.05 mmol to 5 mmol, 0.1 mmol to 2 mmol, 0.1 mmol to 1 mmol, or 0.15 to 0.8 mmol based on 100 g of the total monomer Can be used.

The polymerization in the step (S1) may be anionic polymerization, for example, a living anionic polymerization having an anionic active site at the polymerization end by an anionic growth polymerization reaction. The polymerization in the step (S1) may be an elevated temperature polymerization, an isothermal polymerization or a constant temperature polymerization (adiabatic polymerization), and the above-mentioned constant temperature polymerization may include the step of polymerizing the modifying initiator in its own reaction heat, And the temperature-raising polymerization may mean a polymerization method in which the temperature is increased by applying heat to the modifying initiator after the addition of the modifying initiator. In the isothermal polymerization, after the modifying initiator is charged, heat is applied to heat May be increased or the heat may be taken to maintain the temperature of the polymerizer at a constant level.

According to an embodiment of the present invention, the polymerization in the step (S1) may further include a diene compound having 1 to 10 carbon atoms in addition to the conjugated diene monomer. In this case, There is an effect of preventing the gel from being formed. An example of the diene compound may be 1,2-butadiene.

The polymerization in the step (S1) may be carried out at a temperature of, for example, 80 DEG C or lower, -20 DEG C to 80 DEG C, 0 DEG C to 80 DEG C, 0 DEG C to 70 DEG C, or 10 DEG C to 70 DEG C, The molecular weight distribution of the polymer is narrowly controlled, and the improvement of the physical properties is excellent.

The active polymer produced by the step (S1) may refer to a polymer to which a polymer anion and an organometallic cation are bonded.

According to one embodiment of the present invention, the method for producing the modified conjugated diene-based polymer may be carried out by a continuous polymerization method in a plurality of reactors including two or more polymerization reactors and a denaturing reactor. As a specific example, the step (S1) may be carried out continuously in two or more polymerization reactors including the first reactor, and the number of the polymerization reactors may be determined flexibly according to reaction conditions and environment. The continuous polymerization method may refer to a reaction process in which a reactant is continuously supplied to a reactor and the produced reaction product is continuously discharged. According to the continuous polymerization method, the productivity and processability are excellent and the uniformity of the produced polymer is excellent.

Further, according to one embodiment of the present invention, in continuously producing the active polymer in the polymerization reactor, the polymerization conversion ratio in the first reactor may be 50% or less, 10% to 50%, or 20% to 50% Within this range, it is possible to induce a polymer having a linear structure at the time of polymerization by suppressing a side reaction generated by the formation of the polymer after the initiation of the polymerization reaction within the above range, thereby making it possible to narrow the molecular weight distribution of the polymer, Improvement has an excellent effect.

At this time, the polymerization conversion can be controlled according to the reaction temperature, the residence time of the reactor, and the like.

The polymerization conversion rate can be determined, for example, by measuring the solid concentration on the polymer solution containing the polymer in the polymerization of the polymer. As a concrete example, a cylindrical vessel is mounted at the exit of each polymerization reactor to secure the polymer solution, The polymer solution filled in the cylindrical vessel is placed in an aluminum container, and then the polymer solution is filled in the cylindrical vessel. For example, the weight (B) of a cylindrical container having been transferred to an aluminum dish and from which the polymer solution has been removed is measured, and the aluminum container containing the polymer solution is dried in an oven at 140 캜 for 30 minutes, And may be calculated according to the following equation (1).

[Equation 1]

On the other hand, the polymerized material polymerized in the first reactor is sequentially transferred to the polymerization reactor before the denaturing reactor, and polymerization can proceed until the final polymerization conversion rate reaches 95% or more. After polymerization in the first reactor, , Or from the second reactor to the polymerization reactor before the denatured reactor, the polymerization conversion ratio by each reactor can be appropriately adjusted for each reactor in order to control the molecular weight distribution.

On the other hand, in the step (S1), in the production of the active polymer, the polymer retention time in the first reactor may be 1 minute to 40 minutes, 1 minute to 30 minutes, or 5 minutes to 30 minutes, It is possible to control the conversion rate easily, thereby making it possible to narrow the molecular weight distribution of the polymer. Thus, there is an effect of improving the physical properties.

The term "polymer" in the present invention means that during the step (S1), polymerization is carried out in each reactor before the step (S1) or the step (S2) is completed to obtain an active polymer or a modified conjugated diene polymer , And may mean a polymer having a polymerization conversion of less than 95% in which polymerization is carried out in the reactor.

According to one embodiment of the present invention, the active polymer produced in the step (S1) has a polydispersed index (MWD) of less than 1.5, more than 1.0 and less than 1.5, or 1.1 To less than 1.5, and the modified conjugated diene polymer produced through the modification reaction or coupling with the modifier within this range has a narrow molecular weight distribution and has an excellent effect of improving the physical properties.

The polymerization in the step (S1) may be carried out in the presence of a polar additive. The polar additive may be added in a proportion of 0.001 g to 50 g, 0.001 g to 10 g, or 0.005 g to 0.1 g based on 100 g of the total monomer can do. As another example, the polar additive may be added at a ratio of 0.001 g to 10 g, 0.005 g to 5 g, and 0.005 g to 4 g based on 1 mmol of the total amount of the modifying initiator.

The polar additive may be, for example, at least one selected from the group consisting of tetrahydrofuran, 2,2-di (2-tetrahydrofuryl) propane, diethyl ether, cycloamal ether, dipropyl ether, ethylene methyl ether, ethylene dimethyl ether, diethyl glycol, , Tertiary butoxyethoxyethane, bis (3-dimethylaminoethyl) ether, (dimethylaminoethyl) ethyl ether, trimethylamine, triethylamine, tripropylamine, N, N, N ' And may be at least one selected from the group consisting of ethylenediamine, sodium mentholate and 2-ethyl tetrahydrofuryl ether, preferably 2,2-di (2-tetrahydro (2-ethyl tetrahydrofurfuryl ether), and the polar additive (s) may be selected from the group consisting of sodium chloride, When including the effect of inducing a conjugated diene monomer, or a conjugated diene monomer and aromatic vinyl case of copolymerizing a monomer of these reaction rates so that the random copolymer by giving it up for the difference can be easily formed.

According to an embodiment of the present invention, the reaction or coupling in the step (S2) may be carried out in a denaturing reactor, wherein the modifier is used in an amount of 0.01 mmol to 10 mmol based on 100 g of the total monomer have. As another example, the modifier may be used in a molar ratio of 1: 0.1 to 10, 1: 0.1 to 5, or 1: 0.1 to 1: 3 based on 1 mole of the modifier initiator of the step (S1).

According to an embodiment of the present invention, the denaturant may be introduced into the denaturing reactor, and the step (S2) may be carried out in a denaturing reactor. As another example, the modifier may be added to a transfer part for transferring the active polymer produced in step (S1) to a denaturing reactor for carrying out step (S2), and a mixture of the active polymer and the denaturant in the transfer part Reaction or coupling may proceed.

The method for producing the modified conjugated diene polymer according to one embodiment of the present invention is a method capable of satisfying the characteristics of the above-described modified conjugated diene polymer. The polymerization conversion rate at the time of transferring from the first reactor to the second reactor under the continuous process in the above production method needs to be satisfactory and various polymerization conditions are controlled in other polymerization conditions, The physical properties of the modified conjugated diene polymer according to the present invention can be realized.

In addition, the present invention provides a rubber composition comprising the modified conjugated diene polymer.

The rubber composition may contain the modified conjugated diene polymer in an amount of 10 wt% or more, 10 wt% to 100 wt%, or 20 wt% to 90 wt%, and the tensile strength, abrasion resistance, etc. Is excellent in mechanical properties and excellent in balance among physical properties.

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. As a specific example, the other rubber component 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 polymer.

The rubber component may be, for example, natural rubber or synthetic rubber, and specific examples thereof include natural rubber (NR) containing 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, poly 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.

The rubber composition may include, for example, 0.1 to 200 parts by weight, or 10 to 120 parts by weight of a filler based on 100 parts by weight of the modified conjugated diene polymer of the present invention. The filler may be, for example, a silica-based filler. Specific examples of the filler include wet silica (hydrated silicic acid), dry silica (silicic anhydride), calcium silicate, aluminum silicate or colloidal silica, It can be a wet silica with the most compatible effect of wet grip. In addition, the rubber composition may further include a carbon-based filler, if necessary.

As another example, when silica is used as the filler, a silane coupling agent may be used together with the silane coupling agent for improving the reinforcing property and the low exothermic property. For example, the silane coupling agent may be bis (3-triethoxysilylpropyl) , Bis (3-triethoxysilylpropyl) triesulfide, bis (3-triethoxysilylpropyl) disulfide, bis Propyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 2-mercaptoethyltriethoxysilane, 3-trimethoxysilylpropyl-N, N-dimethylthiocarbamoyltetrasulfide, 3-triethoxysilylpropyl-N, N-dimethylthiocarbamoyltetrasulfide Feed, 2-triethoxysilylethyl-N, N-dimethylthiocarbamoyltetrasulfide, 3-trimethyl 3-triethoxysilylpropylbenzyltetrasulfide, 3-triethoxysilylpropylmethacrylate monosulfide, 3-trimethoxysilylpropylmethacrylate monosulfide, 3-trimethoxysilylpropylmethacrylate monosulfide, , Bis (3-diethoxymethylsilylpropyl) tetrasulfide, 3-mercaptopropyldimethoxymethylsilane, dimethoxymethylsilylpropyl-N, N-dimethylthiocarbamoyltetrasulfide, or dimethoxymethylsilylpropylbenzo Thiazolyl tetrasulfide, etc., and any one or a mixture of two or more thereof may be used. Preferably, it may be bis (3-triethoxysilylpropyl) polysulfide or 3-trimethoxysilylpropylbenzothiazetetrasulfide, considering the effect of improving the reinforcing property.

Further, since the modified conjugated diene polymer in which a functional group having high affinity for silica is introduced into the active site as the rubber component according to an embodiment of the present invention is used, the compounding amount of the silane coupling agent is usually The silane coupling agent may be used in an amount of 1 part by weight to 20 parts by weight, or 5 parts by weight to 15 parts by weight based on 100 parts by weight of silica. Within this range, the effect as a coupling agent is The effect of preventing the gelation of the rubber component is exhibited.

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 contained in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the rubber component. Within this range, the vulcanized rubber composition is required to have the required elastic modulus and strength, It has excellent effect.

The rubber composition according to one embodiment of the present invention may contain various additives commonly used in the rubber industry, such as vulcanization accelerators, process oils, antioxidants, plasticizers, antioxidants, scorch inhibitors, zinc white, stearic acid, a thermosetting resin, or a thermoplastic resin.

Examples of the vulcanization accelerator include thiazole compounds such as M (2-mercaptobenzothiazole), DM (dibenzothiazyl disulfide) and CZ (N-cyclohexyl-2-benzothiazyl sulfenamide) (Diphenylguanidine) may be used, and may be included in an amount of 0.1 to 5 parts by weight based on 100 parts by weight of the rubber component.

The process oil may be a paraffinic, naphthenic, or aromatic compound, which acts as a softening agent in the rubber composition. Considering the aromatic process oil, hysteresis loss, and low temperature characteristics in consideration of tensile strength and abrasion resistance Naphthenic or paraffinic process oils may be used. 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. Within this range, the process oil has an effect of preventing the tensile strength and the low heat build-up (low fuel consumption) of the vulcanized rubber from being lowered.

Examples of the antioxidant include 2,6-di-t-butylparacresol, dibutylhydroxytoluenil, 2,6-bis ((dodecylthio) methyl) (dodecylthio) methyl) -4-nonylphenol or 2-methyl-4,6-bis ((octylthio) methyl) phenol) 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.

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, and 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 the rubber composition using a kneader such as Banbury mixer, roll, internal mixer or the like by the compounding formulation, This excellent rubber composition can be obtained.

Accordingly, the rubber composition can be applied to various members such as tire tread, under-tread, sidewall, carcass coated rubber, belt coated rubber, bead filler, pancake fur, or bead coated rubber, vibration proof rubber, belt conveyor, Can be useful for the production of various industrial rubber products.

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

The tire may be a tire or a tire tread.

Example

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail with reference to examples. However, the embodiments according to the present invention can be modified into various other forms, and the scope of the present invention should not be construed as being limited to the embodiments described below. The embodiments of the present invention are provided to enable those skilled in the art to more fully understand the present invention.

Example  One

3 kg of a styrene solution containing 60% by weight of styrene in n-hexane, 3.0 kg / h of n-hexane, 60% by weight of 1,3-butadiene in n-hexane, (Tetrahydrofuryl) propane dissolved in n-hexane at a concentration of 2% by weight in a polar additive at 12.98 kg / h, n-hexane at 47.14 kg / h, (I) at a rate of 249.2 g / h as a denaturation initiator at 125.0 g / h. At this time, the temperature of the first reactor was kept at 50 ° C, and the polymerization conversion Was 40%, the polymer was transferred from the first reactor to the second reactor through the transfer pipe.

Subsequently, a 1,3-butadiene solution in which 60 wt% of 1,3-butadiene was dissolved in n-hexane was injected into the second reactor at a rate of 0.68 kg / h. At this time, the temperature of the second reactor was maintained at 65 ° C., and when the conversion of polymerization reached 95% or more, the polymer was transferred from the second reactor to the third reactor through the transfer pipe.

(2-methoxyethoxy) ethyl) -3- (triethoxysilyl) propane-1-amine as a modifier was added to the second reactor in a weight ratio of 20 % Was introduced into the third reactor at a rate of 64.0 g / h. The temperature of the third reactor was maintained at 65 ° C.

Thereafter, IR1520 (BASF) solution dissolved at 30 wt% as an antioxidant was injected into the polymerization solution discharged from the third reactor at a rate of 167 g / h and stirred. The resultant polymer was placed in hot water heated with steam and stirred to remove the solvent, thereby preparing a conjugated diene polymer of the same type as that of the end of the end.

(i)

(i)

Example  2

In Example 1, when the polymerization conversion rate reached 42%, the polymerized material was transferred from the first reactor to the second reactor through the transfer pipe, and 3,4-bis (2-methoxyethoxy) -N - (3- (triethoxysilyl) propyl) aniline dissolved in 20 wt% was continuously supplied to the third reactor at a rate of 116.0 g / h. , A hosiery modified conjugated diene polymer was prepared.

Example  3

In Example 1, when the polymerization conversion ratio reached 42%, the polymer was transferred from the first reactor to the second reactor through the transfer pipe, and N, N-bis (3- (triethoxysilyl) propyl ) -2,5,8,11,14-pentaoxahexadecane-16-amine dissolved in 20 wt% was continuously supplied to the third reactor at a rate of 103.5 g / h. The same procedure as in Example 1 was repeated to produce a conjugated diene-based polymer.

Example  4

Except that the polymerizate was transferred from the first reactor to the second reactor through the transfer pipe and the modification initiator (ii) was used in place of the modification initiator (i) when the polymerization conversion rate reached 43% in Example 1 Was carried out in the same manner as in Example 1 to prepare a conjugated diene-based polymer having both ends modified.

(ii)

(ii)

Example  5

A styrene solution containing 60% by weight of styrene in n-hexane at a rate of 6.5 kg / h, n-hexane at 60% by weight of 1,3-butadiene in n-hexane, (Tetrahydrofuryl) propane dissolved in n-hexane to 2% by weight as a polar additive in a concentration of 7.83 kg / h, n-hexane 47.69 kg / (20.0 g / h) as a modifying initiator and 59.0 g / h of a compound represented by the following formula (ii) at a rate of 59.0 g / h. At this time, the temperature of the first reactor was maintained at 50 ° C, Was 40%, the polymer was transferred from the first reactor to the second reactor through the transfer pipe.

Subsequently, a 1,3-butadiene solution in which 60 wt% of 1,3-butadiene was dissolved in n-hexane was injected into the second reactor at a rate of 2.34 kg / h. At this time, the temperature of the second reactor was maintained at 65 ° C., and when the conversion of polymerization reached 95% or more, the polymer was transferred from the second reactor to the third reactor through the transfer pipe.

(2-methoxyethoxy) ethyl) -3- (triethoxysilyl) propane-1-amine as a modifier was added to the second reactor in a weight ratio of 20 % Was introduced into the third reactor at a rate of 64.0 g / h. The temperature of the third reactor was maintained at 65 ° C.

Thereafter, IR1520 (BASF) solution dissolved at 30 wt% as an antioxidant was injected into the polymerization solution discharged from the third reactor at a rate of 167 g / h and stirred. The resultant polymer was placed in hot water heated with steam and stirred to remove the solvent, thereby preparing a conjugated diene polymer of the same type as that of the end of the end.

(ii)

(ii)

Example  6

In Example 5, when the polymerization conversion reached 43%, the polymer was transferred from the first reactor to the second reactor through the transfer pipe, and 3,4-bis (2-methoxyethoxy) -N - (3- (triethoxysilyl) propyl) aniline dissolved in 20 wt% was continuously supplied to the third reactor at a rate of 116.0 g / h. , A hosiery modified conjugated diene polymer was prepared.

Example  7

In Example 5, when the polymerization conversion reached 41%, the polymer was transferred from the first reactor to the second reactor through the transfer pipe, and N, N-bis (3- (triethoxysilyl) propyl ) -2,5,8,11,14-pentaoxahexadecane-16-amine dissolved in 20 wt% was continuously supplied to the third reactor at a rate of 103.5 g / h. The same procedure as in Example 5 was repeated to produce a conjugated diene-based polymer having a hosomodular structure.

Example  8

Except that the polymerizate was transferred from the first reactor to the second reactor through the transfer pipe and the modification initiator (i) was used in place of the modification initiator (ii) when the polymerization conversion rate reached 42% in Example 5 Was carried out in the same manner as in Example 1 to prepare a conjugated diene-based polymer having both ends modified.

(i)

(i)

Comparative Example  One

100 g of styrene, 880 g of 1,3-butadiene, 5000 g of n-hexane and 0.89 g of 2,2-di (2-tetrahydrofuryl) propane as a polar additive were placed in a 20 L autoclave reactor, Lt; 0 &gt; C. When the internal temperature of the reactor reached 50 캜, 4.7 mmol of the compound represented by the above formula (i) was added as a modifying initiator to proceed the adiabatic temperature-rise reaction. After 20 minutes, 20 g of 1,3-butadiene was added to cap the end of the polymer chain with butadiene. After 5 minutes, 4.7 mmol of N, N-bis (2- (2-methoxyethoxy) ethyl) -3- (triethoxysilyl) propane-1-amine was added and reacted for 15 minutes. Thereafter, the polymerization reaction was stopped using ethanol, and 45 ml of a solution in which 0.3 weight% of IR1520 (BASF) was dissolved in n-hexane was added. The resultant polymer was placed in hot water heated with steam and stirred to remove the solvent, thereby preparing a conjugated diene polymer of the same type as that of the end of the end.

Comparative Example  2

3 kg of a styrene solution containing 60% by weight of styrene in n-hexane, 3.0 kg / h of n-hexane, 60% by weight of 1,3-butadiene in n-hexane, (Tetrahydrofuryl) propane dissolved in n-hexane at a concentration of 2% by weight in a polar additive at 12.98 kg / h, n-hexane at 47.14 kg / h, (I) at a rate of 249.2 g / h as a denaturation initiator at 125.0 g / h. At this time, the temperature of the first reactor was maintained at 55 ° C, and the polymerization conversion Was 48%, the polymer was transferred from the first reactor to the second reactor through the transfer pipe.

Subsequently, a 1,3-butadiene solution in which 60 wt% of 1,3-butadiene was dissolved in n-hexane was injected into the second reactor at a rate of 0.68 kg / h. At this time, the temperature of the second reactor was maintained at 65 ° C., and when the conversion of polymerization reached 95% or more, the polymer was transferred from the second reactor to the third reactor through the transfer pipe.

The polymer was transferred from the second reactor to the third reactor, and a solution in which 2 wt% of dichlorodimethylsilane was dissolved in n-hexane as a coupling agent was fed into the third reactor at a rate of 40 g / h. The temperature of the third reactor was maintained at 65 ° C.

Thereafter, IR1520 (BASF) solution dissolved at 30 wt% as an antioxidant was injected into the polymerization solution discharged from the third reactor at a rate of 167 g / h and stirred. The resultant polymer was put into hot water heated with steam and stirred to remove the solvent to prepare an unmodified conjugated diene polymer.

Comparative Example  3

In Example 1, the reaction temperature was maintained at 75 占 폚 in the first reactor, 80 占 폚 in the second reactor, and 80 占 폚 in the third reactor, and when the polymerization conversion rate reached 70% in the first reactor, , And the polymerization was carried out by transferring the polymer from the first reactor to the second reactor to carry out the same processes as in Example 1, to produce a conjugated diene polymer of the same term.

Comparative Example  4

Except that the polymerizate was transferred from the first reactor to the second reactor through the transfer pipe when the polymerization conversion rate reached 45% in Example 1, and the reaction was carried out without introducing the denaturant into the third reactor, The same procedure as in Example 1 was carried out to prepare a terminally stiffened conjugated diene polymer.

Comparative Example  5

An n-butyllithium solution in which 10 wt% of n-butyllithium was dissolved in n-hexane instead of the denaturation initiator (i) in Example 1 was continuously introduced into the first reactor at a rate of 59.0 g / h, When the conversion was 43%, the terminal conjugated diene polymer was prepared in the same manner as in Example 1, except that the polymer was transferred from the first reactor to the second reactor through the transfer pipe.

Comparative Example  6

A styrene solution containing 60% by weight of styrene in n-hexane at a rate of 6.5 kg / h, n-hexane at 60% by weight of 1,3-butadiene in n-hexane, (Tetrahydrofuryl) propane dissolved in n-hexane to 2% by weight as a polar additive in a concentration of 7.83 kg / h, n-hexane 47.69 kg / (I) was fed at a rate of 20.0 g / h as a modifying initiator at a rate of 59.0 g / h. At this time, the temperature of the first reactor was kept at 55 ° C, and the polymerization conversion Was 48%, the polymer was transferred from the first reactor to the second reactor through the transfer pipe.

Subsequently, a 1,3-butadiene solution in which 60 wt% of 1,3-butadiene was dissolved in n-hexane was injected into the second reactor at a rate of 0.74 kg / h. At this time, the temperature of the second reactor was maintained at 65 ° C., and when the conversion of polymerization reached 95% or more, the polymer was transferred from the second reactor to the third reactor through the transfer pipe.

The polymer was transferred from the second reactor to the third reactor, and a solution in which 2 wt% of dichlorodimethylsilane was dissolved in n-hexane as a coupling agent was fed into the third reactor at a rate of 40 g / h. The temperature of the third reactor was maintained at 65 ° C.

Thereafter, IR1520 (BASF) solution dissolved at 30 wt% as an antioxidant was injected into the polymerization solution discharged from the third reactor at a rate of 167 g / h and stirred. The resultant polymer was put into hot water heated with steam and stirred to remove the solvent to prepare an unmodified conjugated diene polymer.

Reference Example  One

In the same manner as in Comparative Example 1, except that 28 mmol of 3- (dimethoxy (methyl) silyl) -N, N-diethylpropan-1- To prepare a diene polymer.

Reference Example  2

The procedure of Comparative Example 1 was repeated except that 1.6 mmol of 3- (dimethoxy (methyl) silyl) -N, N-diethylpropan-1- To prepare a conjugated diene polymer.

Experimental Example  One

The following properties were measured for each of the modified or unmodified conjugated diene-based polymers prepared in the above Examples, Comparative Examples and Reference Examples, and the results are shown in Tables 1 and 2 below.

1) styrene unit and vinyl content (% by weight)

The styrene unit (SM) and vinyl (Vinyl) content in each polymer were measured and analyzed using Varian VNMRS 500 MHz NMR.

In the NMR measurement, 1,1,2,2-tetrachloroethane was used as the solvent. The solvent peak was calculated to be 5.97 ppm, 7.2 to 6.9 ppm for random styrene, 6.9 to 6.2 ppm for block styrene, 5.8 to 5.1 ppm 1,4-vinyl, and 5.1 to 4.5 ppm are 1,2-vinyl peaks, and styrene unit and vinyl content were calculated.

2) The weight average molecular weight (Mw, X10 ³ g / mol), the number average molecular weight (Mn, X10 ³ g / mol), the maximum peak molecular weight (Mp, X10 ³ g / mol) (PDI, MWD)

The weight average molecular weight (Mw), the number average molecular weight (Mn) and the maximum peak molecular weight (Mp) were measured by GPC (Gel Permeation Chromatography) analysis to obtain a molecular weight distribution curve. Further, the molecular weight distributions (PDI, MWD, Mw / Mn) were obtained from the respective molecular weights measured. Specifically, the GPC was prepared by combining two columns of PLgel Olexis (Polymer Laboratories) columns and a column of PLgel mixed-C (Polymer Laboratories) column. In the molecular weight calculation, the GPC standard material was PS (polystyrene) . The GPC measurement solvent was prepared by mixing 2% by weight of an amine compound in tetrahydrofuran. At this time, the obtained molecular weight distribution curve is shown in FIG. 1 to FIG.

In addition, the coupling can have the respective examples and before its use the modifying agent or coupling agent in the comparative examples were collected some polymer to obtain a peak molecular weight (Mp ₁₎ of the polymer, each of the modified conjugated diene-based peak molecular weight of the polymer after (Mp ₂ ) Was obtained and was calculated by the following equation (2).

&Quot; (2) &quot;

Coupling number (CN) = Mp ₂ / Mp ₁

3) Mooney Viscosity and Mooney Relaxation Rate

The Mooney viscosity (MV, (ML1 + 4, @ 100 ° C) MU) was measured using MV-2000 (ALPHA Technologies) at 100 ° C using Rotor Speed 2 ± 0.02 rpm, Large Rotor, The sample was allowed to stand at room temperature (23 ± 3 ° C) for more than 30 minutes, and then 27 ± 3 g was sampled and filled in the die cavity. Platen was operated for 4 minutes.

After measuring the Mooney viscosity, the slope of the Mooney viscosity change as the torque was released was measured to obtain the Mooney relaxation rate.

4) Si content

The Si content was measured using ICP-OES (Optima 7300DV) by ICP analysis method. Specifically, about 0.7 g of a sample was placed in a platinum crucible, and about 1 mL of concentrated sulfuric acid (98% by weight, electronic grade) was added and the mixture was heated at 300 ° C for 3 hours. The sample was placed in an electric furnace (Thermo Scientific, Lindberg &lt; / RTI &gt; Blue &lt; RTI ID = 0.0 &gt; M), &

1) initial temp 0 ° C, rate (temp / hr) 180 ° C / hr, temp (holdtime) 180 ° C (1hr)

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

3) step 3: initial temp 370 ° C, rate (temp / hr) 47 ° C / hr, temp (holdtime) 510 ° C

Add 1 mL of concentrated nitric acid (48% by weight) and 20 μL of concentrated hydrofluoric acid (50% by weight) to the residue. Seal the platinum crucible for 30 minutes or more and shake it. Then add 1 mL of boric acid , Stored at 0 ° C for 2 hours or more, diluted in 30 mL of ultrapure water, and then subjected to painting.

5) N content

N content was measured by NSX analysis method using a Nitrogen Quantitative Analyzer (NSX-2100H). Specifically, a carrier gas flow rate was set at 250 ml / min for Ar, 350 ml / min for O ₂ , and 300 ml / min for an ozonizer by turning on a micro sampler (Horizontal furnace, PMT & Nitrogen detector) Lt; RTI ID = 0.0 &gt; 800 C &lt; / RTI &gt; for about 3 hours to stabilize the analyzer. After the analyzer was stabilized, calibration curves of 5 ppm, 10 ppm, 50 ppm, 100 ppm, and 500 ppm were prepared using the Nitrogen standard (AccuStandard S-22750-01-5 ml) A straight line was created using the ratio of posterior density to area. Then, a ceramic boat containing 20 mg of the sample was placed in an automatic sampler of the analyzer, and the area was measured. The N content was calculated using the area of the obtained sample and the calibration curve.

6) Shrinkage factor (g ')

The shrinkage factor was determined by obtaining an absolute molecular weight from a light scattering detector by injecting a sample into a GPC-light scattering measurement apparatus (Viscotek TDAmax, Malvern) equipped with a light scattering detector and a viscosity detector and measuring intrinsic viscosity [ ], The intrinsic viscosity [?] 0 of the linear polymer with respect to the absolute molecular weight is calculated through the following equation (3), and the intrinsic viscosity [?] / [?] The mean value is expressed as a contraction factor. At this time, the eluent was prepared by mixing 20 mL of a mixed solution of N, N, N ', N'-tetramethylethylenediamine (N, N, N', N'- tetramethylethylenediamine, tetrahydrofuran and 1 L of tetrahydrofuran, ) Was used, and a column was PL Olexix (Agilent). The column was measured at an oven temperature of 40 ° C. and a THF flow rate of 1.0 mL / min. The sample was prepared by dissolving 15 mg of polymer in 10 mL of THF .

&Quot; (3) &quot;

^{_{[η] 0 = 10 -3.883 M}} 0.771

In the above formula (3), M is an absolute molecular weight.

division Example One 2 3 4 5 6 7 8 Reaction conditions Polar additive DTP DTP DTP DTP DTP DTP DTP DTP Initiator a a a b b b b a Denaturants or coupling agents A B C A A B C A M: PI 1: 1 1: 1 1: 1 1: 1 1: 1 1: 1 1: 1 1: 1 First reactor temperature (占 폚) 50 50 50 50 50 50 50 50 The first reactor polymerization conversion ratio (%) 40 42 42 43 40 43 41 42 NMR
(weight%) SM 18 18 18 18 39 39 39 39 Vinyl 47 47 47 47 25 25 25 25 GPC Mw (X10 ³ g / mol) 437 439 452 430 415 419 461 429 Mn (X10 ³ g / mol) 284 283 288 277 261 262 288 270 PDI 1.54 1.55 1.57 1.55 1.59 1.60 1.60 1.59 C.N. 2.20 1.90 1.93 1.95 2.31 1.71 1.68 1.90 Molecular weight distribution curve UNI
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Modal Mooney viscosity (MV) 52 50 53 51 45 47 52 50 Mooney Relaxation Rate (-S / R) 0.798 0.820 0.818 0.810 0.785 0.825 0.830 0.826 The constriction factor (g ') 1.070 1.055 1.060 1.057 1.110 1.112 1.111 1.112 Si content (ppm) 135 132 250 133 135 132 245 133 N content (ppm) 62 59 115 61 62 57 110 60

division Comparative Example Reference Example One 2 3 4 5 6 One 2 Reaction conditions Polar additive DTP DTP DTP DTP DTP DTP DTP DTP Initiator b c a a c c b b Denaturants or coupling agents A D A - A D E E M: PI 1: 1 1: 1 1: 1 - 1: 1 1: 1 5.9: 1 0.3: 1 First reactor temperature (占 폚) 50-> 75 55 75 50 50 55 50-> 75 50-> 75 The first reactor polymerization conversion ratio (%) arrangement 48 70 45 43 48 arrangement arrangement NMR
(weight%) SM 18 18 18 18 18 39 18 18 Vinyl 47 47 47 47 47 25 47 47 GPC Mw (X10 ³ g / mol) 520 476 567 420 441 442 392 550 Mn (X10 ³ g / mol) 356 280 282 284 283 260 280 390 PDI 1.46 1.70 2.01 1.48 1.56 1.70 1.40 1.41 C.N. 1.9 1.50 1.95 - 2.15 1.50 1.0 2.0 Molecular weight distribution curve bye
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Modal Mooney viscosity (MV) 68 54 60 47 53 50 45 65 Mooney mitigation rate 0.52 0.55 0.48 1.48 0.52 0.50 0.65 0.58 The constriction factor (g ') 0.63 0.68 0.62 1.00 0.63 0.60 0.63 0.59 Si content (ppm) 130 30 125 - 123 30 80 75 N content (ppm) 58 - 55 30 53 - 40 35

In Table 1 and Table 2, specific materials of the initiator, the modifier, and the coupling agent are shown in Table 3 below.

Initiator a The compound represented by the formula (i) b The compound represented by the formula (ii) c n-butyllithium Denaturant A N, N-bis (2- (2-methoxyethoxy) ethyl) -3- (triethoxysilyl) propan- B 3,4-bis (2-methoxyethoxy) -N- (3- (triethoxysilyl) propyl) aniline C N, N-bis (3- (triethoxysilyl) propyl) -2,5,8,11,14-pentaoxahexadecane-16-amine D Dichlorodimethylsilane E 3- (dimethoxy (methyl) silyl) -N, N-diethylpropan-1- amine

Referring to Tables 1 and 2, it can be confirmed that the modified conjugated diene polymer of Examples 1 to 8 prepared according to one embodiment of the present invention satisfies all of the required properties. Specifically, it can be predicted that the molecular weight distribution curve is in the form of Unimodal and at the same time, the PDI value is less than 1.7, the formability is remarkably excellent and the compounding property is excellent, and the Mooney relaxation rate is all 0.7 or more, It can be predicted that the shrinkage factor is not less than 0.8 and the balance between physical properties is excellent.

On the other hand, in Comparative Example 3 in which the polymerization conversion rate was not controlled in transferring from the first reactor to the second reactor, the PDI value was high, and the mooney relaxation rate and shrinkage factor were evaluated to be below a specific value, It can be confirmed that the linearity is unsatisfactory.

In addition, when the batch polymerization is applied, it can be predicted that the general modified conjugated diene polymer has a poor PDI value of less than 1.7 but a bimodal molecular weight distribution curve as in Comparative Example 1, and thus the processability is poor. As shown in Reference Examples 1 and 2, a molecular weight distribution curve form of the Unimodule may appear, but this corresponds to the extreme case where the number of couplings is the minimum value or the maximum value, and the modified conjugated diene polymer in such batch polymerization is degraded by the deterioration of the compounding properties Can be found from the above-described contents of the description and evaluation results to be described later.

1 to 4 show the molecular weight distribution curves of Example 1, Comparative Example 1 and Reference Examples 1 and 2, and it can be confirmed that the shape of each molecular weight distribution curve is as described above.

Experimental Example 2

In order to comparatively analyze the physical properties of the rubber compositions comprising the modified or unmodified conjugated diene copolymers prepared in the above Examples, Comparative Examples and Reference Examples and the molded articles produced therefrom, tensile properties and viscoelastic properties were measured The results are shown in Tables 5 and 6 below.

1) Preparation of rubber specimens

The modified or unmodified conjugated diene-based polymers of Examples, Comparative Examples and Reference Examples were compounded under the conditions shown in Table 4 below as raw material rubbers. The content of the raw materials in Table 4 is each parts by weight based on 100 parts by weight of the raw rubber.

division Raw material Content (parts by weight) First stage kneading Rubber 100 Silica 70 Coupling agent (X50S) 11.2 Process oil 37.5 Zinc 3 Stearic acid 2 Antioxidant 2 Antioxidant 2 Wax One Second stage kneading sulfur 1.5 Rubber accelerator 1.75 Vulcanization accelerator 2

Specifically, the rubber specimen is kneaded through the first stage kneading and the second stage kneading. In the first stage kneading, raw rubber, silica (filler), organosilane coupling agent, process oil, zincifying agent, stearic acid, antioxidant, antioxidant and wax were kneaded using a Banbury mixer equipped with a temperature control device. At this time, the initial temperature of the kneader was controlled at 70 占 폚, and a primary blend was obtained at an outlet temperature of 145 占 폚 to 155 占 폚. In the second stage kneading, the above-mentioned primary blend was cooled to room temperature, and then the primary blend, sulfur, rubber promoter and vulcanization accelerator were added to the kneader and mixed at a temperature of 100 DEG C or lower to obtain a second blend. Then, the rubber specimens were prepared by curing at 160 ° C for 20 minutes.

2) Tensile properties

Tensile properties of each test piece were measured 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, the tensile properties were measured at a rate of 50 cm / min at room temperature using a Universal Test Machin 4204 (Instron) tensile tester.

3) Viscoelastic properties

The viscoelastic properties were determined by measuring the viscoelastic behavior of the dynamic deformation at 10 Hz frequency and at each measurement temperature (-60 ℃ ~ 60 ℃) in the film tension mode using a dynamic mechanical analyzer (GABO). The results show that the higher the 0 ° C tan value, the better the wet road surface resistance. The lower the tan δ value at 60 ° C, the lower the hysteresis loss and the better the low resistance (fuel economy).

4) Processability characteristics

The Mooney viscosity (MV, (ML1 + 4, @ 100 ° C) MU) of the second blend obtained in the above 1) rubber specimens was measured to compare the workability characteristics of the respective polymers. And shows excellent workability characteristics.

Specifically, each secondary compound was allowed to stand at room temperature (23 ± 3 ° C) for 30 minutes or more using a MV-2000 (ALPHA Technologies) at a rotor speed of 2 ± 0.02 rpm and a large rotor at 100 ° C., ± 3 g was taken, filled into the die cavity, and platen operated for 4 minutes.

division Example Comparative Example Reference Example One 2 3 4 One 2 3 4 5 One 2 Tensile Properties The tensile strength
(kgf / cm ² ) 188 186 187 192 184 185 184 185 186 185 184 300% modulus
(kgf / cm ² ) 84 83 83 84 75 70 76 77 75 72 73 Viscoelastic properties tan δ
(at 0 C) 102 101 101 101 100 100 101 100 101 100 100 tan δ
(at 60 C) 123 121 120 122 118 100 110 103 105 102 103 Processability 129 127 130 128 140 130 132 120 130 138 142

In Table 5, the results of viscoelastic properties of Examples 1 to 4, Comparative Examples 1 to 3, and Reference Examples 1 and 2 are expressed as indexes (%) based on the measurement value of Comparative Example 2, .

Referring to Table 5, the tensile strengths of Examples 1 to 4, as predicted from the properties of the polymer measured in Experimental Example 1, were at a level equal to or higher than that of Comparative Examples, And the tan δ value at the low temperature was maintained at a level equal to or higher than that of the viscoelastic property, and it was confirmed that the tan δ value at the high temperature was greatly improved. As a result, it was confirmed that the fuel efficiency was improved without loss of the surface resistance I could.

Further, when the polymer produced through the batch polymerization as in Reference Examples 1 and 2 has a unimodal molecular weight distribution curve, it can be seen that the poor processability inherent to the batch polymerization in Reference Example 2 is further exacerbated, In the case of Reference Example 1, it was found that the coupling was not made and the weight average molecular weight was low and the viscosity was low to make the workability excellent. However, it was also confirmed that the tensile characteristic and the viscoelastic characteristic deteriorated remarkably. On the other hand, poor workability inherent to batch polymerization can be confirmed in Comparative Example 1 in which the embodiments according to the present invention and the number of couplings are applied in the same range.

In the case of Comparative Example 3, as a result of not following the manufacturing method of the present invention, the range of the PDI value, the shrinking factor and the Mooney relaxation rate was not satisfied as described above, As shown in FIG. In Comparative Examples 2, 4 and 5 in which the modifier according to the present invention and the modifier initiator were not applied, the viscoelastic characteristics were similarly poor.

division Example Comparative Example 5 6 7 8 6 Tensile Properties Tensile strength (kgf / cm ² ) 188 186 187 186 185 300% modulus (kgf / cm ² ) 102 100 101 101 85 Viscoelastic properties tan δ
(at 0 C) 102 101 100 101 100 tan δ
(at 60 C) 123 120 121 120 100 Processability 120 121 129 127 127

In Table 6, the results of viscoelastic properties of Examples 5 to 8 are expressed as indexes (%) based on the measurement value of Comparative Example 6, and the higher the value, the better.

The results are shown in Table 6. The results are shown in Table 6. The results are shown in Table 6. The results are shown in Table 6. The results are shown in Table 6. It can be seen from Table 6 that the effect is not changed by varying the contents of the monomers, The same result as the improvement result is obtained.

Claims (12)

The molecular weight distribution curve by Gel Permeation Chromatography (GPC) has an unimodal form,
A molecular weight distribution (PDI) (MWD) of 1.0 or more and less than 1.7,
Derived functional group represented by the following general formula (2) or (3) at the other end thereof,
Wherein the modification initiator is a reaction product of a compound represented by the following formula (1) with an organometallic compound:
[Chemical Formula 1]

In Formula 1,
R ₁ to R ₅ independently from each other are hydrogen; An alkyl group having 1 to 30 carbon atoms; An alkenyl group having 2 to 30 carbon atoms; An alkynyl group having 2 to 30 carbon atoms; A heteroalkyl group having 1 to 30 carbon atoms, a heteroalkenyl group having 2 to 30 carbon atoms; A heteroalkynyl group having 2 to 30 carbon atoms; A cycloalkyl group having 5 to 30 carbon atoms; An aryl group having 5 to 30 carbon atoms; Or a heterocyclic group having 3 to 30 carbon atoms,
R ₆ is an alkyl group having 1 to 30 carbon atoms; An alkenyl group having 2 to 30 carbon atoms; An alkynyl group having 2 to 30 carbon atoms; A heteroalkyl group having 1 to 30 carbon atoms, a heteroalkenyl group having 2 to 30 carbon atoms; A heteroalkynyl group having 2 to 30 carbon atoms; A cycloalkyl group having 5 to 30 carbon atoms; An aryl group having 5 to 30 carbon atoms; Or an alkylene group having 1 to 20 carbon atoms which is substituted or unsubstituted with a heterocyclic group having 3 to 30 carbon atoms,
X is a functional group represented by the following formula (1a) or (1b)
[Formula 1a]

In formula (1a)
R ₇ and R ₈ are each independently an alkylene group of 1 to 20 carbon atoms, substituted or unsubstituted with an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or an aryl group having 5 to 20 carbon atoms,
R ₉ is hydrogen; An alkyl group having 1 to 30 carbon atoms; An alkenyl group having 2 to 30 carbon atoms; An alkynyl group having 2 to 30 carbon atoms; A heteroalkyl group having 1 to 30 carbon atoms; A heteroalkenyl group having 2 to 30 carbon atoms; A heteroalkynyl group having 2 to 30 carbon atoms; A cycloalkyl group having 5 to 30 carbon atoms; An aryl group having 5 to 30 carbon atoms; A heterocyclic group having 3 to 30 carbon atoms,
Y is N, O or S atom, and if Y is O or S, R ₉ is not present,
[Chemical Formula 1b]

In the above formula (1b)
R ₁₁ and R ₁₂ independently represent an alkyl group having 1 to 30 carbon atoms; An alkenyl group having 2 to 30 carbon atoms; An alkynyl group having 2 to 30 carbon atoms; A heteroalkyl group having 1 to 30 carbon atoms; A heteroalkenyl group having 2 to 30 carbon atoms; A heteroalkynyl group having 2 to 30 carbon atoms; A cycloalkyl group having 5 to 30 carbon atoms; An aryl group having 5 to 30 carbon atoms; A heterocyclic group having 3 to 30 carbon atoms,
(2)

In Formula 2,
R ₂₀ is a single bond or an alkylene group having 1 to 10 carbon atoms,
R ₂₁ and R ₂₂ are each independently an alkyl group having 1 to 10 carbon atoms or - [R ₄₂ O] _d -R ₄₃ ,
R ₂₃ is a single bond, an alkylene group having 1 to 10 carbon atoms, or - [R ₄₂ O] _d -
R ₂₄ is hydrogen or an alkyl group having 1 to 10 carbon atoms,
R ₄₂ is an alkylene group having 1 to 10 carbon atoms,
R ₄₃ is an alkyl group having 1 to 10 carbon atoms,
a is 2 or 3, c is an integer of 1 to 3, b is an integer of 0 to 2, b + c = 3, d is an integer of 1 to 30,
At least one of R ₂₁ to R ₂₃ necessarily includes the - [R ₄₂ O] _d - unit,
(3)

In Formula 3,
Cy is a trivalent aromatic hydrocarbon group having 6 to 20 carbon atoms or a trivalent heteroaromatic hydrocarbon group having 3 to 20 carbon atoms,
R ₃₀ is a single bond, -NR ₄₄ -, -O-, -S-, or an alkylene group having 1 to 10 carbon atoms,
R ₃₁ and R ₃₂ are each independently an alkyl group having 1 to 10 carbon atoms,
R ₃₃ is - [R ₄₂ O] _d -
R ₃₄ is hydrogen or an alkyl group having 1 to 10 carbon atoms,
R ₄₂ is an alkylene group having 1 to 10 carbon atoms,
R ₄₄ is hydrogen or an alkyl group having 1 to 10 carbon atoms,
m is an integer of 0 to 3, k and n are integers of 1 or 2, k + n = 3, and d is an integer of 1 to 30.
The method according to claim 1,
In Formula 1,
R ₁ to R ₅ independently from each other are hydrogen; An alkyl group having 1 to 10 carbon atoms; An alkenyl group having 2 to 10 carbon atoms; Or an alkynyl group having 2 to 10 carbon atoms,
R ₆ is an unsubstituted alkylene group having 1 to 10 carbon atoms,
X is a functional group represented by the following formula (1a) or (1b)
Wherein R ₇ and R ₈ are each an unsubstituted alkylene group having 1 to 10 carbon atoms; R ₉ is an alkyl group having 1 to 10 carbon atoms; A cycloalkyl group having 5 to 20 carbon atoms; An aryl group having 5 to 20 carbon atoms; Or a heterocyclic group having 3 to 20 carbon atoms, Y is N,
In Formula 1b, R ₁₁ and R ₁₂ independently represent an alkyl group having 1 to 10 carbon atoms; A cycloalkyl group having 5 to 20 carbon atoms; An aryl group having 5 to 20 carbon atoms; Or a heterocyclic group having 3 to 20 carbon atoms.
The method according to claim 1,
In Formula 2,
R ₂₀ is a single bond or an alkylene group having 1 to 5 carbon atoms,
R ₂₁ and R ₂₂ are each independently an alkyl group having 1 to 5 carbon atoms or - [R ₄₂ O] _d -R ₄₃ ,
R ₂₃ is a single bond, an alkylene group having 1 to 5 carbon atoms or - [R ₄₂ O] _d -
R ₂₄ is an alkyl group having 1 to 5 carbon atoms,
R ₄₂ is an alkylene group having 1 to 5 carbon atoms, R ₄₃ is an alkyl group having 1 to 5 carbon atoms,
and d is an integer of 1 to 10.
The method according to claim 1,
Cy is a benzene ring, a pyridine ring, a pyrimidine ring or a triazine ring,
R ₃₀ is -NR ₄₄ -, or an alkylene group having 1 to 5 carbon atoms,
R ₃₁ and R ₃₂ are each independently an alkyl group having 1 to 5 carbon atoms,
R ₃₄ is an alkyl group having 1 to 5 carbon atoms,
R ₄₂ is an alkylene group having 1 to 5 carbon atoms,
R ₄₄ is hydrogen or an alkyl group having 1 to 3 carbon atoms,
and d is an integer of 1 to 10.
The method according to claim 1,
The modified conjugated diene polymer has a number average molecular weight (Mn) of 1,000 g / mol to 2,000,000 g / mol and a weight average molecular weight (Mw) of 1,000 g / mol to 3,000,000 g / mol.
The method according to claim 1,
Wherein the modified conjugated diene polymer has an Si content and an N content of 50 ppm or more based on the weight of the modified conjugated diene polymer, respectively.
The method according to claim 1,
Wherein the modified conjugated diene polymer has a Mooney moderation rate measured at 100 캜 of 0.7 to 3.0.
The method according to claim 1,
Wherein the modified conjugated diene polymer has a shrink factor of 0.8 to 3.0 as measured by a gel permeation chromatography-light scattering method equipped with a viscosity detector.
The method according to claim 1,
Wherein the modified conjugated diene polymer has a coupling number (CN) of 1 < CN < F, wherein F is the number of functional groups of the modifier.
A rubber composition comprising the modified conjugated diene polymer according to claim 1 and a filler.
The method of claim 10,
Wherein the rubber composition comprises 0.1 to 200 parts by weight of a filler based on 100 parts by weight of the modified conjugated diene polymer.
The method of claim 10,
Wherein the filler is a silica-based filler or a carbon-based filler.

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