阅读说明：本技术 改性共轭二烯类聚合物和包含该改性共轭二烯类聚合物的橡胶组合物 (Modified conjugated diene polymer and rubber composition containing same ) 是由 李鲁美 李泰喆 金鲁马 罗六烈 于 2019-07-11 设计创作，主要内容包括：本发明涉及一种改性共轭二烯类聚合物和包含该改性共轭二烯类聚合物的橡胶组合物,更具体地,所述改性共轭二烯类聚合物具有下面i)至v)的条件：i)玻璃化转变温度：-90℃至-50℃,ii)在ASTM D1646条件下测量的门尼粘度：50至100,iii)相对于聚合物的总重量,1,2-乙烯基键含量：30.0重量％以下,iv)分子量分布(PDI；MWD)：1.5至3.5,和v)在110℃下测量的门尼松弛率：0.7以下。(The present invention relates to a modified conjugated diene-based polymer and a rubber composition comprising the same, more specifically, the modified conjugated diene-based polymer has the following conditions i) to v): i) glass transition temperature: -90 ℃ to-50 ℃, ii) mooney viscosity measured under ASTM D1646 conditions: 50 to 100, iii) 1, 2-vinyl bond content relative to the total weight of the polymer: 30.0 wt% or less, iv) molecular weight distribution (PDI; MWD): 1.5 to 3.5, and v) a mooney relaxation rate measured at 110 ℃: 0.7 or less.)

1. A modified conjugated diene-based polymer satisfying the following conditions i) to v):

i) glass transition temperature: from-90 ℃ to-50 ℃,

ii) Mooney viscosity measured under ASTM D1646 condition: from 50 to 100 parts by weight of a polymer,

iii) 1, 2-vinyl bond content relative to the total weight of the polymer: (ii) 30.0% by weight or less,

iv) molecular weight distribution (PDI; MWD): 1.5 to 3.5, and

v) Mooney relaxation rate measured at 110 ℃: 0.7 or less.

2. The modified conjugated diene-based polymer according to claim 1, wherein the glass transition temperature is from-80 ℃ to-50 ℃.

3. The modified conjugated diene polymer according to claim 1, wherein the Mooney viscosity measured under ASTM D1646 is 70 to 100.

4. The modified conjugated diene polymer according to claim 1, wherein the content of 1, 2-vinyl bonds in the polymer is from 5 to 30% by weight.

5. The modified conjugated diene-based polymer according to claim 1, wherein the molecular weight distribution is 1.7 to 2.6.

6. The modified conjugated diene polymer according to claim 1, wherein the Mooney relaxation rate measured at 110 ℃ is 0.45 or less.

7. The modified conjugated diene-based polymer according to claim 1, wherein the modified conjugated diene-based polymer has a number average molecular weight (Mn) of 1,000 to 2,000,000g/mol and a weight average molecular weight (Mw) of 1,000 to 3,000,000 g/mol.

8. The modified conjugated diene-based polymer according to claim 1, wherein the modified conjugated diene-based polymer has an N atom, and the content of the N atom is 50ppm or more with respect to the total weight of the polymer.

9. The modified conjugated diene-based polymer according to claim 1, wherein the modified conjugated diene-based polymer has a Si atom content of 50ppm or more relative to the total weight of the polymer.

10. A rubber composition comprising: the modified conjugated diene-based polymer according to claim 1, and a filler.

11. The rubber composition according to claim 10, wherein the rubber composition contains 0.1 to 200 parts by weight of the filler per 100 parts by weight of the modified conjugated diene-based polymer.

12. The rubber composition according to claim 10, wherein the filler is a silica-based filler or a carbon black-based filler.

Technical Field

[ Cross-reference to related applications ]

This application claims rights based on the priority of korean patent application No.10-2018-0080581, filed on 11.07.2018, and korean patent application No.10-2019-0082689, filed on 09.07.2019, both of which are incorporated herein by reference in their entirety.

Background

In accordance with recent demand for automobiles with low fuel consumption rates, conjugated diene-based polymers having modulation stability represented by wet skid resistance and low rolling resistance as well as excellent abrasion resistance and tensile properties are required as rubber materials for tires.

In order to reduce the rolling resistance of a tire, there is a method of reducing the hysteresis loss of a vulcanized rubber, and rebound resilience, tan, Goodrich heat generation (Goodrich heating) at 50 to 80 ℃ and the like are used as evaluation indexes of the vulcanized rubber. That is, it is desirable to use a rubber material having high resilience or low tan value or Goodrich heat generation at the above-mentioned temperature.

Natural rubber, polyisoprene rubber or polybutadiene rubber is known as a rubber material having low hysteresis loss, but these rubbers have a limitation of low wet skid resistance. Therefore, recently, conjugated diene-based polymers or copolymers such as styrene-butadiene rubber (hereinafter referred to as "SBR") and butadiene rubber (hereinafter referred to as "BR") are produced by emulsion polymerization or solution polymerization for use as rubber for tires. Among these polymerization methods, the solution polymerization has the greatest advantage over the emulsion polymerization that the vinyl structure content and styrene content, which determine the physical properties of the rubber, can be arbitrarily adjusted, and the molecular weight and physical properties thereof can be controlled by coupling or modification. Therefore, SBR prepared by solution polymerization is widely used as a rubber material for tires because it easily changes the structure of SBR or BR finally prepared, and the movement of chain ends can be reduced and the coupling force with fillers such as silica and carbon black can be increased by coupling or modification of the chain ends.

If solution polymerized SBR is used as a rubber material for tires, since the glass transition temperature of rubber is increased with increasing vinyl content in SBR, physical properties required for tires such as running resistance and braking force can be controlled, and fuel consumption can be reduced by appropriately adjusting the glass transition temperature. The solution-polymerized SBR is prepared by using an anionic polymerization initiator, and is used by coupling or modifying chain ends of the polymer thus formed using various modifying agents. For example, U.S. Pat. No.4,397,994 discloses a method of coupling living anions at the chain ends of polymers obtained by polymerizing styrene-butadiene in a nonpolar solvent using an alkyllithium as a monofunctional initiator using a coupling agent such as a tin compound.

Disclosure of Invention

Technical problem

The present invention is designed to solve the above-mentioned problems of the conventional techniques and to provide a modified conjugated diene-based polymer capable of improving rolling resistance and abrasion resistance of a final tire and improving processability during mixing by controlling the glass transition temperature, 1, 2-vinyl bond content, mooney viscosity and branching degree of the modified conjugated diene-based polymer.

Technical scheme

In order to solve the above-mentioned task, according to one embodiment of the present invention, there is provided a modified conjugated diene-based polymer satisfying the following conditions i) to v): i) glass transition temperature: -90 ℃ to-50 ℃, ii) mooney viscosity measured under ASTM D1646 conditions: 50 to 100, iii) 1, 2-vinyl bond content relative to the total weight of the polymer: 30.0 wt% or less, iv) molecular weight distribution (PDI; MWD): 1.5 to 3.5, and v) a mooney relaxation rate measured at 110 ℃: 0.7 or less.

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

Advantageous effects

The modified conjugated diene-based polymer according to the present invention has a high degree of branching while satisfying a glass transition temperature and a 1, 2-vinyl bond content within specific ranges, and can have excellent rolling resistance and abrasion resistance and improved processability even at a high degree of branching by having a mooney viscosity controlled to an appropriate level.

Detailed Description

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

It should be understood that the words or terms used in the specification and claims of this invention should not be construed as meanings defined in commonly used dictionaries. It should also be understood that these words or terms should be interpreted as having meanings consistent with their meanings in the technical idea of the present invention on the basis of the principle that the inventor can appropriately define the meanings of the words or terms to best explain the invention.

Definition of

The term "polymer" used in the present disclosure refers to a polymer compound prepared by polymerizing monomers, regardless of the same or different kinds of monomers. Also, the generic term polymer refers to polymers prepared from only one monomer and includes the common terms homopolymer and copolymer.

The term "vinyl content" as used in this disclosure refers to the mass (or weight) percentage of butadiene contained in the polymer in the 1-and 2-positions of the polymer chain based on the conjugated diene monomer (butadiene, etc.) portion (based on the total weight of the polymerized butadiene).

In the present invention, the term "monovalent hydrocarbon group" may refer to a monovalent radical obtained by bonding carbon and hydrogen in monovalent alkyl groups, alkenyl groups, alkynyl groups, cycloalkyl groups containing one or more unsaturated bonds, and aryl groups. The minimum carbon number of the substituent represented by the monovalent hydrocarbon may be determined according to the kind of each substituent.

In the present invention, the term "divalent hydrocarbon group" may refer to a divalent radical obtained by bonding carbon and hydrogen in a divalent alkylene group, alkenylene group, alkynylene group, cycloalkylene group containing one or more unsaturated bonds, and arylene group. The minimum carbon number of the substituent represented by the divalent hydrocarbon may be determined according to the kind of each substituent.

In the present invention, the term "alkyl group" may refer to a monovalent aliphatic saturated hydrocarbon, and may include both straight-chain alkyl groups such as methyl, ethyl, propyl, and butyl, and branched-chain alkyl groups such as isopropyl, sec-butyl, tert-butyl, and neopentyl.

In the present invention, the term "alkenyl group" may refer to a monovalent aliphatic unsaturated hydrocarbon comprising one or two or more double bonds.

In the present invention, the term "alkynyl group" may refer to a monovalent aliphatic unsaturated hydrocarbon containing one or two or more triple bonds.

In the present invention, the term "alkylene group" may refer to a divalent aliphatic saturated hydrocarbon such as methylene, ethylene, propylene and butylene.

In the present invention, the term "aryl group" may refer to cyclic aromatic hydrocarbons, and may include both monocyclic aromatic hydrocarbons forming one ring and polycyclic aromatic hydrocarbons in which two or more rings are combined.

In the present invention, the term "heterocyclic group" is obtained by substituting carbon atoms in a cycloalkyl group or an aryl group with one or more hetero atoms, and may refer to both a heterocycloalkyl group and a heteroaryl group.

The terms "comprising" and "having," as well as derivatives thereof, in this disclosure are not intended to exclude the presence of optional additional elements, steps, or processes, whether or not the terms are specifically disclosed. In order to avoid any uncertainty, all compositions claimed through use of the term "comprising" may contain optional additional additives, adjuvants or compounds, including polymers or any other substances, unless stated to the contrary. In contrast, the term "consisting essentially of …" does not include elements that are not necessary for operation, and excludes optional other elements, steps, or processes from the scope of the optional following description. The term "consisting of …" excludes optional elements, steps or processes not specifically described or shown.

Measurement method and conditions

In the present disclosure, "glass transition temperature (Tg)" is obtained as follows: the modified conjugated diene-based polymer was regarded as a test sample, helium gas was supplied at a rate of 50ml/min using a differential scanning calorimeter (product name "DSC 3200S", manufactured by MacScience corporation) based on ISO 22768:2006, a DSC curve was recorded while raising the temperature from-100 ℃ at a rate of 10 ℃/min, and the peak top (inflection point) of the DSC differential curve was measured as the glass transition temperature.

In the present invention, "1, 2-vinyl bond content" was measured and analyzed using a Varian VNMRS 500MHz NMR, and the 1, 2-vinyl bond content in the entire polymer was calculated and measured by using 1,1,2, 2-tetrachloroethane as a solvent in the course of measuring NMR, and 6.0ppm was calculated as a solvent peak, 7.2ppm to 6.9ppm was calculated as a random styrene peak, 6.9ppm to 6.2ppm was calculated as a block styrene peak, 5.8ppm to 5.1ppm was calculated as 1, 4-vinyl and 1, 2-vinyl peaks, and 5.1ppm to 4.5ppm was calculated as a 1, 2-vinyl peak.

In the present disclosure, "weight average molecular weight (Mw)", "number average molecular weight (Mn)" and "Molecular Weight Distribution (MWD)" are measured by Gel Permeation Chromatography (GPC) analysis, and are measured by checking a molecular weight distribution curve molecular weight distribution (PDI, MWD, Mw/Mn) is calculated from each measured molecular weight, specifically, GPC uses two P L gel oxides columns (Polymer L alloys Co.) and one P L gel mixed-C column (Polymer L alloys Co.) in combination, and uses Polystyrene (PS) as a GPC standard substance for calculating molecular weight, and uses tetrahydrofuran mixed with 2 wt% of an amine compound as a GPC measurement solvent.

In the present disclosure, for measuring "Mooney Viscosity (MV)" and "Mooney relaxation rate (-S/R)," Mooney viscosity (MV, (M L1 +4, @100 ℃ MU) was measured at 100 ℃ using a large rotor at a rotor rotation speed of 2 + -0.02 rpm using MV-2000(Alpha Technologies Co.). in this case, the used sample was left at room temperature (23 + -3 ℃) for 30 minutes or more, and 27 + -3 g of the sample was collected and put into a mold cavity, and then, a platen was operated for 4 minutes for measurement.

In the present disclosure, "Si content" is measured using inductively coupled plasma emission spectrometry (ICP-OES; Optima7300DV), which is an ICP analysis method, if inductively coupled plasma emission spectrometry is used, the measurement is performed by adding about 0.7g of a sample to a platinum (Pt) crucible, adding about 1M L of concentrated sulfuric acid (98 wt%, electronic grade) thereto, heating at 300 ℃ for 3 hours, and burning the sample in an electric furnace (Thermo Scientific, L indeberg Blue M) by the following procedure of step 1 to step 3:

1) step 1: the initial temperature was 0 ℃, the rate (temperature/hour) was 180 ℃/hour, the temperature (holding time) was 180 ℃ (1 hour),

2) step 2: the initial temperature was 180 ℃, the rate (temperature/hour) was 85 ℃/hour, the temperature (hold time) was 370 ℃ (2 hours),

3) and step 3: the initial temperature was 370 ℃, the rate (temperature/hour) was 47 ℃/hour, the temperature (hold time) was 510 ℃ (3 hours),

to the residue were added 1m L concentrated nitric acid (48 wt%) and 20 μ l concentrated hydrofluoric acid (50 wt%), the platinum crucible was sealed and shaken for 30 minutes or more, 1m L boric acid was added to the sample, stored at 0 ℃ for 2 hours or more, diluted in 30ml of ultrapure water, and incinerated.

In the present disclosure, the "N content" may be measured by, for example, an NSX analysis method, and the measurement of the NSX analysis method may be performed using a quantitative analyzer of trace nitrogen (NSX-2100H). For example, in the case of a quantitative analyzer using trace nitrogen, the quantitative analyzer for trace nitrogen (autosampler, horizontal furnace, PMT) is turned on&Nitrogen detector) with the carrier gas flow set to Ar of 250ml/min, O₂350ml/min, 300ml/min ozone generator, heater set to 800 ℃, and analyzer held for about 3 hours to stabilize. After the analyzer was stabilized, calibration curves ranging from 5ppm, 10ppm, 50ppm, 100ppm and 500ppm were prepared using nitrogen standards (AccuStandard S-22750-01-5ml), and areas corresponding to the respective concentrations were obtained. Then, a straight line is made using the ratio of the concentration to the area. Thereafter, the ceramic boat containing 20mg of the sample was placed in an autosampler of an analyzer and measured to obtain an area. The N content was calculated using the area of the thus obtained sample and the calibration curve. In this case, the sample is a modified conjugated diene-based polymer from which the solvent is removed by placing the sample in hot water heated by steam and stirring, and may be a sample from which the remaining monomer, the remaining modifier, and the oil are removed.

Modified conjugated diene polymer

The modified conjugated diene-based polymer according to the present invention is a modified conjugated diene-based polymer satisfying the following conditions i) to v): i) glass transition temperature: -90 ℃ to-50 ℃, ii) mooney viscosity measured under ASTM D1646 conditions: 50 to 100, iii) 1, 2-vinyl bond content relative to the total weight of the polymer: 30.0 wt% or less, iv) molecular weight distribution (PDI; MWD): 1.5 to 3.5, and v) a mooney relaxation rate measured at 110 ℃: 0.7 or less.

According to an embodiment of the present invention, the modified conjugated diene-based polymer may include a repeating unit derived from a conjugated diene-based monomer and a functional group derived from a modifying agent. The repeating unit derived from the conjugated diene-based monomer may refer to a repeating unit formed from the conjugated diene-based monomer during polymerization, and the functional group derived from the modifying agent may refer to a functional group derived from the modifying agent which is present at one end of the living polymer by reaction or coupled between the living polymer and the modifying agent.

According to an embodiment of the present invention, the conjugated diene monomer may be one or more selected from the group consisting of 1, 3-butadiene, 2, 3-dimethyl-1, 3-butadiene, piperylene, 3-butyl-1, 3-octadiene, isoprene, 2-phenyl-1, 3-butadiene and 2-halo-1, 3-butadiene (halo means a halogen atom).

Meanwhile, the modified conjugated diene-based polymer may be a copolymer including a repeating unit derived from an aromatic vinyl monomer, and may include 30% by weight or more or 30% by weight to 50% by weight of the repeating unit derived from an aromatic vinyl monomer. Within the range, an excellent balance effect between rolling resistance and wet skid resistance can be obtained.

The aromatic vinyl monomer may be, for example, one or more selected from the group consisting of styrene, α -methylstyrene, 3-methylstyrene, 4-propylstyrene, 1-vinylnaphthalene, 4-cyclohexylstyrene, 4- (p-methylphenyl) styrene and 1-vinyl-5-hexylnaphthalene.

In another embodiment, the modified conjugated diene-based polymer may be a copolymer further comprising a repeating unit derived from a diene-based monomer of 1 to 10 carbon atoms, together with the repeating unit derived from the conjugated diene-based monomer. The repeating unit derived from a diene-based monomer 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, for example, 1, 2-butadiene. If the modified conjugated diene-based polymer is a copolymer further containing a diene-based monomer, the modified conjugated diene-based 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 of a repeating unit derived from a diene-based monomer, within which range an effect of preventing formation of gel may be obtained.

According to an embodiment of the present invention, the copolymer may be a random copolymer, and in this case, an excellent balance effect between physical properties may be obtained. Random copolymers may refer to a random arrangement of repeating units that form the copolymer.

The modified conjugated diene-based polymer according to one embodiment of the present invention is required to satisfy a glass transition temperature of-90 ℃ to-50 ℃, preferably, -80 ℃ to-50 ℃. The glass transition temperature may vary depending on the amount of the aromatic vinyl monomer as a comonomer, but is not determined only by the amount of the comonomer, but may vary depending on the polymerization method and conditions. That is, the modified conjugated diene-based polymer prepared to satisfy the above range has excellent affinity with a filler such as silica and carbon black during mixing, and abrasion resistance thereof can be improved. If the glass transition temperature is higher than-50 ℃, tensile properties such as abrasion resistance may be reduced, if the glass transition temperature is lower than-90 ℃, processability may be deteriorated, and it is understood that viscoelastic properties such as rolling resistance and wet skid resistance may be reduced. Therefore, it is preferable to satisfy the above range.

In addition, the modified conjugated diene-based polymer according to one embodiment of the present invention is required to satisfy a mooney viscosity of 50 to 100, specifically, 70 to 100, preferably, 70 to 90 if measured under the condition of astm d 1646. The measure for evaluating the processability may be various, but if the mooney viscosity satisfies the above range, the processability becomes very excellent.

Meanwhile, in general, in the glass transition temperature range of-90 ℃ to-50 ℃, the mooney viscosity is difficult to satisfy the above range, but according to the present invention, the branching degree of the modified conjugated diene-based polymer can be increased by controlling the polymerization method and conditions, whereby the modified conjugated diene-based polymer satisfying the glass transition temperature, the mooney viscosity and the mooney relaxation rate in the above range can be provided.

In addition, the modified conjugated diene-based polymer according to one embodiment of the present invention is required to satisfy the 1, 2-vinyl bond content of 30% by weight or less with respect to the total weight of the polymer. The vinyl content may mean the weight% of the 1, 4-addition but 1, 2-addition conjugated diene monomer with respect to 100% by weight of the conjugated diene copolymer composed of the monomer having a vinyl group and the aromatic vinyl monomer, and may be affected by the termination point of the polymerization reaction, the reaction environment at the termination point of the polymerization reaction, and the like during the polymerization.

Specifically, the 1, 2-vinyl bond content may be 5 to 30% by weight, preferably 5 to 15% by weight, and the abrasion property and the rolling resistance property may be affected according to the 1, 2-vinyl bond content. If the content of the 1, 2-vinyl bond is more than 30% by weight, the glass transition temperature may be affected, and thus, the abrasion property may be drastically deteriorated. Therefore, in the production of the modified conjugated diene-based polymer, attention needs to be paid to the reaction conditions so that the 1, 2-vinyl bond content satisfies the above-mentioned range.

The modified conjugated diene-based polymer according to one embodiment of the present invention may have a number average molecular weight (Mn) of 1,000 to 2,000,000g/mol, 10,000 to 1,000,000g/mol, or 100,000 to 800,000g/mol, and a weight average molecular weight (Mw) of 1,000 to 3,000,000g/mol, 10,000 to 2,000,000g/mol, or 100,000 to 1,500,000g/mol, if measured by Gel Permeation Chromatography (GPC). Within the above range, excellent rolling resistance and wet skid resistance effects can be obtained.

In another embodiment, the modified conjugated diene-based polymer may have a molecular weight distribution (PDI; MWD; Mw/Mn) of 1.5 to 3.5, preferably, 1.5 to 3.0, or 1.7 to 2.6, and in this range, an excellent effect of a balance between tensile properties, viscoelastic properties, and physical properties may be obtained.

In addition, the modified conjugated diene-based polymer has a molecular weight distribution curve of a monomodal shape or a bimodal shape by Gel Permeation Chromatography (GPC), and the monomodal and bimodal curve shapes can be determined in view of continuous and batch polymerization methods, and in view of modification reaction by a modifier or a coupling agent.

The Mooney relaxation rate of the modified conjugated diene-based polymer measured at 110 ℃ can be an index of the degree of branching and the molecular weight of the corresponding modified conjugated diene-based copolymer. The modified conjugated diene polymer may have a Mooney relaxation rate at 110 ℃ of 0.7 or less, preferably 0.6 or less, more preferably 0.5 or less, most preferably 0.45 or less. Further, the mooney relaxation rate may mean an increase in the branching degree and the molecular weight, and the lower limit thereof is not particularly limited, but may be preferably 0.05 or more. The mooney relaxation rate of the modified conjugated diene-based polymer according to the present invention may be 0.7 or less, and the effect of this embodiment may be exhibited.

As described above, the mooney relaxation rate of the modified conjugated diene-based polymer measured at 110 ℃ can be an index of the branching degree and molecular weight of the modified conjugated diene-based polymer, and the branching degree and molecular weight of the modified conjugated diene-based polymer tend to increase as the mooney relaxation rate decreases. However, in general, the Mooney relaxation rate will be related to the Mooney viscosity. For the modified conjugated diene-based polymer having the same degree of mooney viscosity, the mooney relaxation rate decreases as the branching increases, and therefore, for the case of having the same mooney viscosity, it can be used as a linearity index.

The mooney relaxation rate of 0.7 or less can be obtained by, for example, controlling the weight average molecular weight to a mooney viscosity range of the modified conjugated diene-based polymer of 70 to 100, and controlling the branching degree of the polymer thus produced, that is, by increasing the branching degree in the case where the weight average molecular weight is decreased, and decreasing the branching degree in the case where the weight average molecular weight is increased, or by the number of functional groups of the modifier, the addition amount of the modifier, or the degree of metallization.

The modified conjugated diene-based polymer according to one embodiment of the present invention may have an N content and an Si content of 25ppm or more, 50ppm or more, 70ppm to 10,000ppm or 100ppm to 5,000ppm, respectively, on a weight basis, and within the ranges, a rubber composition comprising the modified conjugated diene-based polymer has an effect of exhibiting excellent mechanical properties such as tensile properties and viscoelastic properties. The N content and the Si content may refer to the amount of N atoms and the amount of Si atoms present in the modified conjugated diene-based polymer, respectively. Meanwhile, the N atom and the Si atom may be derived from a modifier.

Meanwhile, the modified conjugated diene-based polymer according to an embodiment of the present invention may have a modification ratio of 30% or more.

In addition, the modified conjugated diene-based polymer may have a modification ratio of 50% or more, and in the case where the N atom content and the Si atom content are 25ppm or more (on a weight basis), the modification ratio may be 30% or more. The modification ratio does not vary depending on the N atom content and the Si atom content, but may partially vary depending on the content.

However, in the modification reaction, the N atom content and the Si atom content and the modification ratio may exhibit partial independence according to the degree of coupling by the modifier, and in order to obtain a high modification ratio of 50% or more, preferably 55% or more or 60% or more, and optimally 70% or more, it is necessary to reduce the amount of the polymer coupled during the modification reaction, which may be controlled by the addition amount of the modifier, the amount of the polar additive, the reaction time, the mixing time and the mixing degree of the modifier and the living polymer, and the like.

As described above, if the modified conjugated diene-based polymer according to the present invention satisfies the above conditions, abrasion resistance and rolling resistance during mixing can be greatly improved due to increased affinity with fillers such as silica and carbon black, and processability can be improved as physical properties are improved. Further, in the case of a modified conjugated diene-based polymer which additionally satisfies the condition of the modification ratio, the wet skid resistance can be improved together with the abrasion resistance and rolling resistance, and therefore, a modified conjugated diene-based polymer which can greatly improve the tensile properties and viscoelastic properties can be provided.

The modifier according to the present invention may be a modifier for modifying the terminal of the conjugated diene-based polymer, and specifically, may be a modifier having affinity with silica. The modifying agent having affinity with silica may refer to a modifying agent containing a functional group having affinity with silica in a compound used as the modifying agent, and the functional group having affinity with silica may refer to a functional group which has excellent affinity with a filler, specifically, a silica-based filler, and is capable of causing interaction between the silica-based filler and the functional group derived from the modifying agent.

The modifier may be, for example, a modifier of the alkoxysilane type, specifically, a modifier of the alkoxysilane type containing one or more hetero atoms including a nitrogen atom, an oxygen atom and a sulfur atom. If the alkoxysilane-based modifier is used, one end of the living polymer can be modified into a state of being bonded to the silyl group by a substitution reaction between the anion reactive moiety located at one end of the living polymer and the alkoxy group of the alkoxysilane-based modifier, and therefore, the affinity of the functional group derived from the modifier present at one end of the modified conjugated diene-based polymer with the inorganic filler can be increased, and the mechanical properties of the rubber composition containing the modified conjugated diene-based polymer can be improved. Further, if the alkoxysilane-based modifier contains a nitrogen atom, an additional effect of improving physical properties due to the nitrogen atom can be expected in addition to the effect from the silyl group.

According to an embodiment of the present invention, the modifier may include a compound represented by formula 1 below:

[ formula 1]

In formula 1, R¹May be a single bond or alkylene of 1 to 10 carbon atoms, R²And R³May each independently be an alkyl group of 1 to 10 carbon atoms, R⁴Can be hydrogen, alkyl of 1 to 10 carbon atoms, divalent, trivalent or substituted by alkyl of 1 to 10 carbon atomsTetravalent alkylsilyl groups, or heterocycles of 2 to 10 carbon atoms, R²¹May be a single bond, alkylene of 1 to 10 carbon atoms or- [ R ]⁴²O]_j-, in which R⁴²May be an alkylene group of 1 to 10 carbon atoms, a and m may each independently be an integer selected from 1 to 3, n may be an integer of 0, 1 or 2, and j may be an integer selected from 1 to 30.

In a specific embodiment, in formula 1, R¹May be a single bond or alkylene of 1 to 5 carbon atoms, R²And R³May each independently be hydrogen, alkyl of 1 to 5 carbon atoms, R⁴May be hydrogen, alkyl of 1 to 5 carbon atoms, tetravalent alkylsilyl substituted with alkyl of 1 to 5 carbon atoms or heterocycle of 2 to 5 carbon atoms, R²¹May be a single bond, alkylene of 1 to 5 carbon atoms or- [ R ]⁴²O]_j-, in which R⁴²May be an alkylene group of 1 to 5 carbon atoms, a may be an integer of 2 or 3, m may be an integer selected from 1 to 3, and n may be an integer of 0, 1 or 2, wherein m + n ═ 3 may be satisfied, and j may be an integer selected from 1 to 10.

In formula 1, if R⁴Is a heterocyclic ring, the heterocyclic ring may be unsubstituted or substituted with a trisubstituted alkoxysilyl group, if the heterocyclic ring is substituted with a trisubstituted alkoxysilyl group, the trisubstituted alkoxysilyl group may be substituted with an alkylene group of 1 to 10 carbon atoms by being linked to the heterocyclic ring, and the trisubstituted alkoxysilyl group may refer to an alkoxysilyl group substituted with an alkoxy group of 1 to 10 carbon atoms.

In a more specific embodiment, the compound represented by formula 1 may be selected from the group consisting of N, N-bis (3- (dimethoxy (methyl) silyl) propyl) -methyl-1-amine, N-bis (3- (diethoxy (methyl) silyl) propyl) -methyl-1-amine, N-bis (3- (trimethoxysilyl) propyl) -methyl-1-amine, N-bis (3- (triethoxysilyl) propyl) -methyl-1-amine, N-diethyl-3- (trimethoxysilyl) propan-1-amine, N-diethyl-3- (triethoxysilyl) propan-1-amine, N-bis (3- (triethoxysilyl) propan-, Tris (trimethoxysilyl) amine, tris- (3- (trimethoxysilyl) propyl) amine, N-bis (3- (diethoxy (methyl) silyl) propyl) -1,1, 1-trimethylsilylamine, N-bis (3- (1H-imidazol-1-yl) propyl) - (triethoxysilyl) methane-1-amine, N- (3- (1H-1,2, 4-triazol-1-yl) propyl) -3- (trimethoxysilyl) -N- (3- (trimethoxysilyl) propyl) propan-1-amine, 3- (trimethoxysilyl) -N- (3- (trimethoxysilyl) propyl) -N- (3- (1- (3- (trimethoxysilyl) propyl) amine - (trimethoxysilyl) propyl) -1H-1,2, 4-triazol-3-yl) propyl) propan-1-amine, N-bis (2- (2-methoxyethoxy) ethyl) -3- (triethoxysilyl) propan-1-amine, N-bis (3- (triethoxysilyl) propyl) -2,5,8,11, 14-pentaoxahexadecan-16-amine, N- (2,5,8,11, 14-pentaoxahexadecan-16-yl) -N- (3- (triethoxysilyl) propyl) -2,5,8,11, 14-pentaoxahexadecan-16-amine and N- (3,6,9, 12-tetraoxahexadecyl) -N- (3- (triethoxysilyl) propyl) -3,6,9, 12-tetraoxahexadecan-1-amine.

In another embodiment, the modifier may include a compound represented by formula 2 below:

[ formula 2]

In formula 2, R⁵、R⁶And R⁹May each independently be an alkylene group of 1 to 10 carbon atoms, R⁷、R⁸、R¹⁰And R¹¹May each independently be an alkyl group of 1 to 10 carbon atoms, R¹²May be hydrogen or alkyl of 1 to 10 carbon atoms, b and c may each independently be 0, 1,2 or 3, where b + c ≧ 1, A may beOrWherein R is¹³、R¹⁴、R¹⁵And R¹⁶May each independently be hydrogen or an alkyl group of 1 to 10 carbon atoms.

In a specific embodiment, the compound represented by formula 2 may be one selected from the group consisting of N- (3- (1H-imidazol-1-yl) propyl) -3- (triethoxysilyl) -N- (3- (triethoxysilyl) propyl) propan-1-amine and 3- (4, 5-dihydro-1H-imidazol-1-yl) -N, N-bis (3- (triethoxysilyl) propyl) propan-1-amine.

In another embodiment, the modifier may include a compound represented by the following formula 3:

[ formula 3]

In formula 3, A¹And A²May each independently be a divalent hydrocarbon group of 1 to 20 carbon atoms with or without oxygen atoms, R¹⁷To R²⁰May each independently be a monovalent hydrocarbon group of 1 to 20 carbon atoms, L¹To L⁴May each independently be a divalent, trivalent or tetravalent alkylsilyl group substituted with an alkyl group of 1 to 10 carbon atoms, or a monovalent hydrocarbon group of 1 to 20 carbon atoms, wherein L¹And L²And L³And L⁴Can be combined with each other to form a ring of 1 to 5 carbon atoms if L¹And L²And L³And L⁴Form a ring in combination with each other, and the ring thus formed may contain one to three heteroatoms selected from N, O and S.

In a specific embodiment, in formula 3, A¹And A²May each independently be an alkylene group of 1 to 10 carbon atoms, R¹⁷To R²⁰May each independently be an alkyl group of 1 to 10 carbon atoms, L¹To L⁴May each independently be a tetravalent alkylsilyl group substituted with an alkyl group of 1 to 5 carbon atoms, or an alkyl group of 1 to 10 carbon atoms, wherein, L¹And L²And L³And L⁴Can be combined with each other to form a ring of 1 to 3 carbon atoms if L¹And L²And L³And L⁴Form a ring by binding to each other, and the ring thus formed may contain one selected from N, O and SFrom one to three heteroatoms.

In a more specific embodiment, the compound represented by formula 3 may be selected from 3,3'- (1,1,3, 3-tetramethoxydisiloxane-1, 3-diyl) bis (N, N-dimethylpropane-1-amine), 3,3' - (1,1,3, 3-tetraethoxydisiloxane-1, 3-diyl) bis (N, N-dimethylpropane-1-amine), 3,3'- (1,1,3, 3-tetrapropoxydisiloxane-1, 3-diyl) bis (N, N-dimethylpropane-1-amine), 3,3' - (1,1,3, 3-tetramethoxydisiloxane-1, 3-diyl) bis (N, N-diethylpropane-1-amine), 3,3' - (1,1,3, 3-tetramethoxydisiloxane-1, 3-diyl) bis (N, N-dipropylpropane-1-amine), 3,3' - (1,1,3, 3-tetraethoxydisiloxane-1, 3-diyl) bis (N, N-diethylpropane-1-amine), 3,3' - (1,1,3, 3-tetrapropoxydisiloxane-1, 3-diyl) bis (N, N-diethylpropane-1-amine), 3,3' - (1,1,3, 3-tetraethoxydisiloxane-1, 3-diyl) bis (N, N-dipropylpropane-1-amine), 3,3' - (1,1,3, 3-tetrapropoxydisiloxane-1, 3-diyl) bis (N, N-dipropylpropane-1-amine), 3,3'- (1,1,3, 3-tetramethoxydisiloxane-1, 3-diyl) bis (N, N-diethylmethane-1-amine), 3,3' - (1,1,3, 3-tetraethoxydisiloxane-1, 3-diyl) bis (N, N-diethylmethane-1-amine), 3,3'- (1,1,3, 3-tetrapropoxydisiloxane-1, 3-diyl) bis (N, N-diethylmethane-1-amine), 3,3' - (1,1,3, 3-tetramethoxydisiloxane-1, 3-diyl) bis (N, N-dimethylmethane-1-amine), 3,3'- (1,1,3, 3-tetramethoxydisiloxane-1, 3-diyl) bis (N, N-dipropylmethane-1-amine), 3,3' - (1,1,3, 3-tetrapropoxydisiloxane-1, 3-diyl) bis (N, N-dimethylmethane-1-amine), 3,3'- (1,1,3, 3-tetrapropoxydisiloxane-1, 3-diyl) bis (N, N-dipropylmethane-1-amine), 3,3' - (1,1,3, 3-tetraethoxydisiloxane-1, 3-diyl) bis (N, N-dimethylmethane-1-amine), 3,3'- (1,1,3, 3-tetraethoxydisiloxane-1, 3-diyl) bis (N, N-dipropylmethane-1-amine), N' - ((1,1,3, 3-tetramethoxydisiloxane-1, 3-diyl) bis (propane-3, 1-diyl)) bis (1,1, 1-trimethyl-N- (trimethylsilyl) silanamine), N '- ((1,1,3, 3-tetraethoxydisiloxane-1, 3-diyl) bis (propane-3, 1-diyl)) bis (1,1, 1-trimethyl-N- (trimethylsilyl) silanamine), N' - ((1,1,3, 3-tetrapropoxydisiloxane-1, 3-diyl) bis (propane-3, 1-diyl)) bis (1,1, 1-trimethyl-N- (trimethylsilyl) silanylamine), N ' - ((1,1,3, 3-tetramethoxydisiloxane-1, 3-diyl) bis (propane-3, 1-diyl)) bis (1,1, 1-trimethyl-N-phenylsilamine), N ' - ((1,1,3, 3-tetraethoxydisiloxane-1, 3-diyl) bis (propane-3, 1-diyl)) bis (1,1, 1-trimethyl-N-phenylsilamine), N ' - ((1,1,3, 3-tetrapropoxydisiloxane-1, 3-diyl) bis (propane-3), 1-diyl)) bis (1,1, 1-trimethyl-N-phenylsilane amine), 1, 3-bis (3- (1H-imidazol-1-yl) propyl) -1,1,3, 3-tetramethoxydisiloxane, 1, 3-bis (3- (1H-imidazol-1-yl) propyl) -1,1,3, 3-tetraethoxydisiloxane, and 1, 3-bis (3- (1H-imidazol-1-yl) propyl) -1,1,3, 3-tetrapropoxydisiloxane.

In another embodiment, the modifier may include a compound represented by formula 4 below:

[ formula 4]

In formula 4, R²²And R²³May each independently be an alkylene group of 1 to 20 carbon atoms, or-R²⁸[OR²⁹]_f-，R²⁴To R²⁷May each independently be an alkyl group of 1 to 20 carbon atoms or an aryl group of 6 to 20 carbon atoms, R²⁸And R²⁹May each independently be an alkylene group of 1 to 20 carbon atoms, R⁴⁷And R⁴⁸May be each independently a divalent hydrocarbon group of 1 to 6 carbon atoms, d and e may be each independently 0 or an integer selected from 1 to 3, wherein d + e may be an integer of 1 or more, and f may be an integer of 1 to 30.

Specifically, in formula 4, R²²And R²³May each independently be an alkylene group of 1 to 10 carbon atoms, or-R²⁸[OR²⁹]_f-，R²⁴To R²⁷May each independently be an alkyl group of 1 to 10 carbon atoms, R²⁸And R²⁹May be each independently an alkylene group of 1 to 10 carbon atoms, d and e may each independently be 0 or an integer selected from 1 to 3, wherein d + e may be an integer of 1 or more, and f may be an integer of 1 to 30.

More specifically, the compound represented by formula 4 may be a compound represented by formula 4a, formula 4b, or formula 4c below:

[ formula 4a ]

[ formula 4b ]

[ formula 4c ]

In the formulae 4a, 4b and 4c, R²²To R²⁷D and e are the same as described above.

In a more specific embodiment, the compound represented by formula 4 may be selected from the group consisting of 1, 4-bis (3- (3- (triethoxysilyl) propoxy) propyl) piperazine, 1, 4-bis (3- (triethoxysilyl) propyl) piperazine, 1, 4-bis (3- (trimethoxysilyl) propyl) piperazine, 1, 4-bis (3- (dimethoxymethylsilyl) propyl) piperazine, 1- (3- (ethoxydimethylsilyl) propyl) -4- (3- (triethoxysilyl) propyl) piperazine, 1- (3- (ethoxydimethyl) propyl) -4- (3- (triethoxysilyl) methyl) piperazine, 1- (3- (ethoxydimethyl) methyl) -4- (3- (triethoxysilyl) methyl) piperazine, and one of alkyl) propyl) piperazine, 1, 3-bis (3- (triethoxysilyl) propyl) imidazolidine, 1, 3-bis (3- (dimethoxyethylsilyl) propyl) imidazolidine, 1, 3-bis (3- (trimethoxysilyl) propyl) hexahydropyrimidine, 1, 3-bis (3- (triethoxysilyl) propyl) hexahydropyrimidine, and 1, 3-bis (3- (tributoxysilyl) propyl) -1,2,3, 4-tetrahydropyrimidine.

In another embodiment, the modifier may include a compound represented by the following formula 5:

[ formula 5]

In formula 5, R³⁰May be a monovalent hydrocarbon group of 1 to 30 carbon atoms, R³¹To R³³May each independently be an alkylene group of 1 to 10 carbon atoms, R³⁴To R³⁷May be each independently an alkyl group of 1 to 10 carbon atoms, and g and h may each independently be 0 or an integer selected from 1 to 3, wherein g + h may be an integer of 1 or more.

In another embodiment, the modifier may include a compound represented by the following formula 6:

[ formula 6]

In formula 6, A³And A⁴May each independently be an alkylene group of 1 to 10 carbon atoms, R³⁸To R⁴¹May each independently be an alkyl group of 1 to 10 carbon atoms or an alkoxy group of 1 to 10 carbon atoms, and i may be an integer selected from 1 to 30.

In another embodiment, the modifier may comprise a compound selected from the group consisting of 3, 4-bis (2-methoxyethoxy) -N- (4- (triethoxysilyl) butyl) aniline, N, one or more of N-diethyl-3- (7-methyl-3, 6,8, 11-tetraoxa-7-silatridecan-7-yl) propan-1-amine, 2, 4-bis (2-methoxyethoxy) -6- ((trimethylsilyl) methyl) -1,3, 5-triazine, and 3, 14-dimethoxy-3, 8,8, 13-tetramethyl-2, 14-dioxa-7, 9-dithia-3, 8, 13-trisilapentadecane.

In another embodiment, the modifier may include a compound represented by the following formula 7:

[ formula 7]

In formula 7, R⁴³、R⁴⁵And R⁴⁶May each independently be an alkyl group of 1 to 10 carbon atoms, R⁴⁴May be an alkylene group of 1 to 10 carbon atoms, and k may be selected from 1 to 4Is an integer of (1).

In a more specific embodiment, the compound represented by formula 7 may be selected from the group consisting of 8, 8-dibutyl-3, 13-dimethoxy-3, 13-dimethyl-2, 14-dioxa-7, 9-dithia-3, 13-disila-8-stannopentadecane, 8-dimethyl-3, 13-dimethoxy-3, 13-dimethyl-2, 14-dioxa-7, 9-dithia-3, 13-disila-8-stannopentadecane, 8-dibutyl-3, 3,13, 13-tetramethoxy-2, 14-dioxa-7, 9-dithia-3, 13-disila-8-stannopentadecane and 8-butyl-3, 3,13, 13-tetramethoxy-8- ((3- (trimethoxysilyl) propyl) thio) -2, 14-dioxa-7, 9-dithia-3, 13-disiloxa-8-stannopentadecane.

Method for preparing modified conjugated diene polymer

In order to produce the modified conjugated diene-based polymer, the present invention provides a method for producing a modified conjugated diene-based polymer. The method for producing the modified conjugated diene-based polymer may include: a step (S1) of polymerizing the conjugated diene monomer in a hydrocarbon solvent in the presence of an organometallic compound to prepare an organometallic-coupled living polymer; and a step (S2) of reacting the living polymer prepared in the step (S1) with a modifier, wherein the polymerization reaction (S1) and the modification reaction (S2) are performed by a continuous type or a batch type.

Hereinafter, the characteristics of the modified conjugated diene-based polymer thus prepared and the modifier used in the reaction overlap with the above description, and the description thereof will be omitted.

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

According to an embodiment of the present invention, the organometallic compound may be used in an amount of 0.01mmol to 10mmol, 0.05mmol to 5mmol, 0.1mmol to 2mmol, 0.1mmol to 1mmol, or 0.15mmol to 0.8mmol, based on a total of 100g of the monomers. The organometallic compound may be, for example, one or more selected from methyllithium, ethyllithium, propyllithium, isopropyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, hexyllithium, n-decyllithium, tert-octyllithium, phenyllithium, 1-naphthyllithium, n-eicosyllithium, 4-butylphenyl lithium, 4-methylphenyllithium, cyclohexyllithium, 3, 5-di-n-heptylcyclohexyllithium, 4-cyclopentyllithium, sodium naphthylate, potassium naphthylate, lithium alkoxide, sodium alkoxide, potassium alkoxide, lithium sulfonate, sodium sulfonate, potassium sulfonate, lithium amide, sodium amide, potassium amide, and lithium isopropylamide.

The polymerization of step (S1) may be, for example, anionic polymerization, specifically, living anionic polymerization in which an anionic living moiety is formed at the polymerization terminal by a propagation reaction of an anion. Further, the polymerization of step (S1) may be polymerization accompanied by heating, isothermal polymerization, or constant temperature polymerization (adiabatic polymerization). Here, the isothermal polymerization refers to a polymerization method comprising a step of performing polymerization using heat generated by the reaction itself without optionally supplying heat after adding an organometallic compound, and the polymerization accompanied by heating refers to a polymerization method comprising adding an organometallic compound and then increasing the temperature by optionally supplying heat. Isothermal polymerization refers to a polymerization process in which the temperature of a polymer is kept constant by adding heat or removing heat through supply of heat after addition of an organometallic compound.

In addition, according to an embodiment of the present invention, the polymerization of step (S1) may be carried out by adding a diene compound of 1 to 10 carbon atoms in addition to the conjugated diene monomer, and in this case, an effect of preventing gel formation on the wall of the reactor during a long-term operation may be obtained. The diene-based compound may include, for example, 1, 2-butadiene.

The polymerization of step (S1) may be performed at a temperature ranging from 100 ℃ or less, from 50 ℃ to 100 ℃, or from 50 ℃ to 80 ℃. Within the range, the conversion rate of the polymerization reaction can be increased, the glass transition temperature, the mooney viscosity, and the 1, 2-vinyl bond content can be satisfied within the above ranges while controlling the molecular weight distribution of the polymer, and the effect of improving physical properties can be excellent.

The living polymer prepared by the step (S1) may refer to a polymer in which a polymer anion is coupled with an organometallic cation.

According to an embodiment of the present invention, the living polymer prepared by the polymerization of step (S1) may be a random copolymer, and in this case, an excellent balance effect between the respective physical properties may be obtained. Random copolymers may refer to a random arrangement of repeating units that form the copolymer.

The term "polymerization reactant" used in the present invention may refer to an intermediate of a polymer type in which polymerization is performed in each reactor during the step (S1) being performed, or may refer to a polymer in which polymerization conversion rate of polymerization performed in a reactor is less than 90% after the step (S1) or the step (S2) is completed and before a living polymer or a modified conjugated diene-based polymer is obtained.

Meanwhile, the polymerization of step (S1) may be performed by including a polar additive, and the polar additive may be added in a ratio of 0.001g to 50g or 0.002g to 0.1g based on a total of 100g of the monomers. In another embodiment, the polar additive may be added in a ratio of 0g to 1g, 0.01g to 1g, or 0.1g to 0.9g, based on a total of 100g of the organometallic compound. In the case of adding the polar additive within the above-mentioned range, the glass transition temperature, the Mooney viscosity and the 1, 2-vinyl bond content within the above-mentioned ranges may be satisfied.

The polar additive may be, for example, one or more selected from tetrahydrofuran, di (tetrahydrofuryl) propane, diethyl ether, cyclopentyl ether, dipropyl ether, ethylene methyl ether, ethylene dimethyl ether, ethylene glycol, dimethyl ether, t-butoxyethoxyethane, bis (3-dimethylaminoethyl) ether, (dimethylaminoethyl) ethyl ether, trimethylamine, triethylamine, tripropylamine, and tetramethylethylenediamine, and may preferably be triethylamine or tetramethylethylenediamine. If the polar additive is contained, and if the conjugated diene-based monomer, or the conjugated diene-based monomer and the aromatic vinyl-based monomer are copolymerized, the difference in the reaction rates thereof can be compensated, and an effect of causing easy formation of a random copolymer can be obtained.

According to an embodiment of the present invention, in the reaction of step (S2), the modifier may be used in an amount of 0.01mmol to 10mmol based on a total of 100g of the monomers. In another embodiment, 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 1mol of the organometallic compound in step (S1). The molar ratio of the modifier to the organometallic compound, and the amount of the modifier added relative to the monomer can greatly affect the glass transition temperature, the mooney viscosity, and the mooney relaxation rate of the polymer thus produced, and suitable proportions within the above ranges can be preferably selected and used, if possible.

In addition, according to an embodiment of the present invention, the modifier may be added to the modification reactor, and the step (S2) may be performed in the modification reactor. In another embodiment, the modifier may be added to a transfer part for transferring the living polymer prepared in the step (S1) to the modification reactor to perform the step (S2), and the reaction may be performed by mixing the living polymer with the modifier in the transfer part. In this case, the reaction may be a modification reaction simply coupling the modifying agent with the living polymer, or a coupling reaction based on the linking of the modifying agent to the living polymer, and the ratio of the modification reaction to the coupling reaction needs to be controlled as described above, which affects the mooney viscosity and mooney relaxation rate and glass transition temperature.

Meanwhile, in the production process according to one embodiment of the present invention, control of the glass transition temperature, the mooney viscosity, the mooney relaxation rate, and the 1, 2-vinyl bond content of the modified conjugated diene-based polymer thus produced may be affected depending on the kind and amount of the organometallic compound, the kind and amount of the polar additive, the kind and amount of the modifier, and the temperature and time of the polymerization reaction and the modification reaction, and therefore, the production process according to the present invention may be carried out by organically appropriately controlling under the above-mentioned conditions to satisfy the conditions of the modified conjugated diene-based polymer proposed in the present invention.

According to the present invention, there is provided a rubber composition comprising the modified conjugated diene-based polymer.

The rubber composition may contain 10% by weight or more, 10% by weight to 100% by weight, or 20% by weight to 90% by weight of the modified conjugated diene-based polymer, and within the range, mechanical properties such as tensile strength and abrasion resistance are excellent, and an effect of an excellent balance between physical properties may be achieved.

In addition, the rubber composition may contain other rubber components as needed in addition to the modified conjugated diene-based polymer, and in this case, the content of the rubber component may be 90% by weight or less based on the total weight of the rubber composition. In a specific embodiment, the content of the rubber component may be 1 part by weight to 900 parts by weight based on 100 parts by weight of the modified conjugated diene-based copolymer.

The rubber component may be, for example, natural rubber or synthetic rubber, and may be specifically Natural Rubber (NR) including cis-1, 4-polyisoprene; modified natural rubber obtained by modifying or purifying conventional natural rubber, such as Epoxidized Natural Rubber (ENR), deproteinized natural rubber (DPNR) and hydrogenated natural rubber; and synthetic rubbers such as styrene-butadiene copolymer (SBR), polybutadiene (BR), polyisoprene (IR), butyl rubber (IIR), ethylene-propylene copolymer, polyisobutylene-isoprene copolymer, chloroprene rubber, poly (ethylene-propylene copolymer), poly (styrene-butadiene copolymer), poly (styrene-isoprene-butadiene copolymer), poly (ethylene-propylene-diene copolymer), polysulfide rubber, acrylic rubber, polyurethane rubber, silicone rubber, epichlorohydrin rubber, butyl rubber and halogenated butyl rubber, and any one or a mixture of two or more thereof may be used.

The rubber composition may contain 0.1 to 200 parts by weight or 10 to 120 parts by weight of the filler, based on 100 parts by weight of the modified conjugated diene-based polymer of the present invention. The filler may be, for example, a silica-based filler, specifically, wet silica (hydrated silicate), dry silica (anhydrous silicate), calcium silicate, aluminum silicate, or colloidal silica. Preferably, the filler may be wet silica having the most remarkable improvement effect of the deterioration property and the compatible effect of the wet adhesion. Further, the rubber composition may further contain a carbon-based filler, as required.

In another embodiment, if silica is used as the filler, a silane coupling agent may be used together to improve the reinforcing and low heat release properties. Specific examples of the silane coupling agent may include: bis (3-triethoxysilylpropyl) tetrasulfide, bis (3-triethoxysilylpropyl) trisulfide, bis (3-triethoxysilylpropyl) disulfide, bis (2-triethoxysilylethyl) tetrasulfide, bis (3-trimethoxysilylpropyl) tetrasulfide, bis (2-trimethoxysilylethyl) tetrasulfide, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyltriethoxysilane, 3-trimethoxysilylpropyl-N, N-dimethylthiocarbamoyl tetrasulfide, 3-triethoxysilylpropyl-N, N-dimethylthiocarbamoyl tetrasulfide, and mixtures thereof, 2-triethoxysilylethyl-N, N-dimethylthiocarbamoyl tetrasulfide, 3-trimethoxysilylpropylbenzothiazolyl tetrasulfide, 3-triethoxysilylpropylbenzoyl tetrasulfide, 3-triethoxysilylpropylmethacrylate monosulfide, 3-trimethoxysilylpropyl methacrylate monosulfide, bis (3-diethoxymethylsilylpropyl) tetrasulfide, 3-mercaptopropyldimethoxymethylsilane, dimethoxymethylsilylpropyl-N, N-dimethylthiocarbamoyl tetrasulfide or dimethoxymethylsilylpropylbenzothiazolyl tetrasulfide, and any one or a mixture of two or more thereof may be used. Preferably, in view of the property-enhancing improvement effect, bis (3-triethoxysilylpropyl) polysulfide or 3-trimethoxysilylpropylbenzothiazolyl tetrasulfide may be used.

In addition, in the rubber composition according to one embodiment of the invention, since the modified conjugated diene-based polymer in which a functional group having high affinity with silica is introduced at an active site is used as a rubber component, the blending amount of the silane coupling agent can be smaller than that in the conventional case. Therefore, the silane coupling agent may be used in an amount of 1 to 20 parts by weight or 5 to 15 parts by weight, based on 100 parts by weight of silica. Within the above amount range, the effect as a coupling agent can be sufficiently exhibited, and the effect of preventing gelation of the rubber component can be obtained.

The rubber composition according to one embodiment of the present invention may be sulfur crosslinkable and thus may further contain a vulcanizing agent. The vulcanizing agent may specifically be sulfur powder, and the content thereof may be 0.1 parts by weight to 10 parts by weight based on 100 parts by weight of the rubber component. Within the above range, the elasticity and strength required for the vulcanized rubber composition can be secured, and at the same time, an excellent low fuel consumption rate can be obtained.

The rubber composition according to one embodiment of the present invention may further contain various additives used in the conventional rubber industry, in particular, a vulcanization accelerator, a processing oil, a plasticizer, an age resistor, an anti-scorching agent, zinc white, stearic acid, a thermosetting resin or a thermoplastic resin, in addition to the above-mentioned ingredients.

The vulcanization accelerator may include, for example, thiazole compounds such as 2-mercaptobenzothiazole (M), dibenzothiazyl Disulfide (DM) and N-cyclohexyl-2-benzothiazylsulfenamide (CZ); or a guanidine compound such as Diphenylguanidine (DPG), and may be contained in an amount of 0.1 to 5 parts by weight, based on 100 parts by weight of the rubber component.

The processing oil acts as a softener in the rubber composition and may include, for example, paraffins, naphthenes, or aromatics. An aromatic processing oil may be used in consideration of tensile strength and abrasion resistance, and a naphthenic or paraffinic processing oil may be used in consideration of hysteresis loss and low-temperature properties. The content of the processing oil may be 100 parts by weight or less based on 100 parts by weight of the rubber component. Within the above range, the deterioration of the tensile strength and low heat release performance (low fuel consumption rate) of the vulcanized rubber can be prevented.

The age resistor may include, for example, N-isopropyl-N '-phenyl-p-phenylenediamine, N- (1, 3-dimethylbutyl) -N' -phenyl-p-phenylenediamine, 6-ethoxy-2, 2, 4-trimethyl-1, 2-dihydroquinoline, or a condensate of diphenylamine and acetone at a high temperature, and may be used in an amount of 0.1 to 6 parts by weight, based on 100 parts by weight of the rubber component.

The rubber composition according to one embodiment of the present invention can be obtained by mixing according to the mixing formulation using a mixing device such as a Banbury mixer, a roll and an internal mixer. By the vulcanization process after the molding process, a rubber composition having low heat release properties and good abrasion properties can be obtained.

Thus, the rubber composition can be used for manufacturing various members of a tire, such as a tire tread, a tread base, a sidewall, a carcass coating rubber, a belt coating rubber, a bead filler, a chafer and a bead coating rubber, or for manufacturing rubber products in various industries, such as a vibration damping rubber, a conveyor belt and a hose.

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

The tire may be a tire or include a tire tread.