WO2024225378A1 - 共役ジエン系重合体、共役ジエン系重合体の製造方法 - Google Patents

共役ジエン系重合体、共役ジエン系重合体の製造方法 Download PDF

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WO2024225378A1
WO2024225378A1 PCT/JP2024/016246 JP2024016246W WO2024225378A1 WO 2024225378 A1 WO2024225378 A1 WO 2024225378A1 JP 2024016246 W JP2024016246 W JP 2024016246W WO 2024225378 A1 WO2024225378 A1 WO 2024225378A1
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conjugated diene
polymer
diene polymer
glass transition
mass
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English (en)
French (fr)
Japanese (ja)
Inventor
孝顕 牛尾
裕太 橋爪
ダビデ ダルアバコ
ルチア リータ ルビーノ
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Asahi Kasei Corp
Asahi Chemical Industry Co Ltd
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Asahi Kasei Corp
Asahi Chemical Industry Co Ltd
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Priority to JP2025516886A priority Critical patent/JP7815549B2/ja
Priority to KR1020257015039A priority patent/KR20250084290A/ko
Priority to CN202480006246.1A priority patent/CN120513264A/zh
Priority to EP24797123.7A priority patent/EP4703396A1/en
Publication of WO2024225378A1 publication Critical patent/WO2024225378A1/ja
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F136/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F136/02—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F136/04—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
    • C08F136/06—Butadiene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
    • C08C19/00—Chemical modification of rubber
    • C08C19/25—Incorporating silicon atoms into the molecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
    • C08C19/00—Chemical modification of rubber
    • C08C19/22—Incorporating nitrogen atoms into the molecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
    • C08F236/06—Butadiene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
    • C08F236/10—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated with vinyl-aromatic monomers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/42—Introducing metal atoms or metal-containing groups

Definitions

  • the present invention relates to a conjugated diene polymer and a method for producing a conjugated diene polymer.
  • Wet grip performance which is a required characteristic of rubber to provide braking performance on wet roads
  • low temperature performance which is a required characteristic of rubber to provide braking performance on snow
  • Tire tread rubber is required to resolve this conflict between these properties.
  • rubber compositions that reduce the elastic modulus at low temperatures to improve low-temperature performance and ensure high conformability of the tread rubber to snowy road surfaces have been known, and technology has been proposed to lower the glass transition temperature of rubber materials in order to lower the glass transition temperature of rubber compositions.
  • Patent Document 1 discloses a rubber composition containing silica and a modified conjugated diene polymer with a low glass transition temperature obtained by reacting an alkoxysilane containing an amino group with the active end of a conjugated diene polymer, and proposes a technology for improving low-temperature performance.
  • Patent Document 2 discloses a rubber composition containing a conjugated diene polymer with a high glass transition temperature and silica, and proposes a technology for improving wet grip performance.
  • the present invention aims to provide a conjugated diene polymer that can provide a tire with excellent wet grip performance and low temperature performance, and a method for producing the conjugated diene polymer.
  • the present invention is as follows.
  • the estimated glass transition temperature (estimated Tg) derived from the microstructure of the conjugated diene polymer is ⁇ 72° C. or higher and ⁇ 45° C. or lower, has only one glass transition temperature (Tg) as measured by differential scanning calorimetry (DSC);
  • the conjugated diene polymer has a glass transition temperature (Tg) in which the difference between an extrapolated glass transition onset temperature and an extrapolated glass transition end temperature is 15°C or more and 35°C or less.
  • [3] The conjugated diene polymer according to [1] or [2] above, wherein the molecular weight distribution, which is the ratio Mw/Mn of the weight average molecular weight Mw to the number average molecular weight Mn, is 1.7 or more and 2.5 or less.
  • the segment ratio of the first polymer segment is 20% by mass or more and 80% by mass or less.
  • [5] The conjugated diene polymer according to any one of [1] to [4] above, having a weight average molecular weight of 300,000 or more and 1,350,000 or less.
  • [8] A method for producing the conjugated diene polymer according to any one of [2] to [7], Using two or more continuous reactors, a first polymerization step (P1) of continuously forming a first polymer segment of a conjugated diene-based polymer by adding a conjugated diene compound, a polymerization initiator, and a polar substance to the continuous reactor; a second polymerization step (P2) in which an aromatic vinyl compound and a polar substance are added to the continuous reactor to form a second polymer segment at an end of the first polymer segment; having, A method for producing a conjugated diene polymer.
  • the present invention provides a conjugated diene polymer whose vulcanizate combines excellent wet grip performance and low temperature performance.
  • the present embodiment an embodiment of the present invention (hereinafter, referred to as "the present embodiment") will be described in detail.
  • the following embodiments are merely illustrative for explaining the present invention, and are not intended to limit the present invention to the following contents.
  • the present invention can be modified appropriately within the scope of the gist thereof.
  • conjugated diene polymer contains conjugated diene monomer units and aromatic vinyl monomer units.
  • the conjugated diene polymer of the present embodiment has an estimated glass transition temperature (hereinafter, may be referred to as estimated Tg) derived from the microstructure in the conjugated diene polymer of -72°C or more and -45°C or less.
  • estimated Tg estimated glass transition temperature
  • the estimated glass transition temperature (estimated Tg) is derived from the microstructure of the conjugated diene polymer, as described later.
  • the conjugated diene-based polymer of the present embodiment has only one glass transition temperature (Tg) measured by differential scanning calorimetry (DSC), and the difference between the extrapolated glass transition onset temperature and the extrapolated glass transition end temperature of the glass transition temperature (Tg) is 15° C. or more and 35° C. or less.
  • Conjugated diene compounds forming the conjugated diene monomer units include, but are not limited to, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 3-methyl-1,3-pentadiene, 1,3-hexadiene, and 1,3-heptadiene.
  • 1,3-butadiene and isoprene are preferred from the viewpoint of industrial availability. These may be used alone or in combination of two or more.
  • the conjugated diene compound is preferably 1,3-butadiene or isoprene, and more preferably 1,3-butadiene.
  • aromatic vinyl compounds examples include, but are not limited to, styrene, p-methylstyrene, ⁇ -methylstyrene, vinylethylbenzene, vinylxylene, vinylnaphthalene, and diphenylethylene.
  • styrene is preferred from the viewpoint of industrial availability. These compounds may be used alone or in combination of two or more.
  • aromatic vinyl compounds styrene is preferred from the viewpoints of availability and ease of structural control during polymer synthesis.
  • the microstructure refers to a polymer composition including the distinction between isomers in a conjugated diene-based polymer using an aromatic vinyl compound and a conjugated diene compound or in a polymer segment described below.
  • the mass of the copolymer consisting of styrene and butadiene is preferably 70 mass% or more, more preferably 80 mass% or more, and even more preferably 90 mass% or more, based on the mass of the entire conjugated diene polymer.
  • the estimated Tg of the conjugated diene polymer of the present embodiment is derived from the microstructure of the conjugated diene polymer, and one example of the microstructure is the amount of bound aromatic vinyl monomer units (X all ).
  • the amount of bound aromatic vinyl monomer units (X all ) (mass %) refers to the mass fraction of bound aromatic vinyl monomer units relative to the total mass of the conjugated diene polymer of this embodiment.
  • the amount of bound aromatic vinyl monomer units can be calculated by measuring the ultraviolet absorption of the phenyl group of the portion of the conjugated diene polymer derived from the aromatic vinyl compound (hereinafter, sometimes referred to as "bound aromatic vinyl monomer units" or "aromatic vinyl monomer units").
  • bound aromatic vinyl monomer units or "aromatic vinyl monomer units”
  • the amount of bound conjugated diene monomer units can be obtained from the amount of bound aromatic vinyl monomer units obtained as described above. Specifically, it can be measured by the method described in the examples below.
  • the estimated Tg of the conjugated diene polymer of the present embodiment is derived from the microstructure of the conjugated diene polymer, and an example of the microstructure is the amount of vinyl bonds (Y all ) in the bound conjugated diene.
  • the vinyl bond amount (Y all ) (mol %) in the bound conjugated diene is the molar fraction (mol %) of 1,2-bond units relative to the polymerization units derived from the conjugated diene compound contained in the conjugated diene-based polymer of the present embodiment.
  • the amount of vinyl bonds in the bound conjugated diene can be obtained by determining the amount of vinyl bonds (1,2-bond amount) in the bound butadiene by the Hampton method (R.R. Hampton, Analytical Chemistry, 21, 923 (1949)). Specifically, it can be measured by the method described in the examples below.
  • the conjugated diene polymer of the present embodiment preferably has a small number of blocks in which four or more bound aromatic vinyl monomer units are chained (hereinafter, may be referred to as bound aromatic vinyl monomer unit blocks) or no blocks.
  • bound aromatic vinyl monomer unit blocks a small number of blocks in which four or more bound aromatic vinyl monomer units are chained
  • no blocks a small number of blocks in which four or more bound aromatic vinyl monomer units are chained
  • the content of the bound aromatic vinyl monomer unit block in the conjugated diene polymer, when the conjugated diene polymer is a butadiene-styrene polymer, can be measured by a known method in which the conjugated diene polymer is decomposed by the Kolthoff method (method described in I.M. KOLTHOFF, et al., J. Polym. Sci. 1, 429 (1946)) and the amount of polystyrene insoluble in methanol is analyzed.
  • the content of the bound aromatic vinyl monomer unit block measured by such a method is preferably 1.0 mass% or less, more preferably 0.1 mass% or less, based on the total amount of the conjugated diene polymer.
  • the conjugated diene copolymer and the polymer segment described below do not contain the bound aromatic vinyl monomer unit block, the conjugated diene polymer of this embodiment tends to show continuous properties with respect to temperature change. As a result, the vulcanizate using the conjugated diene polymer of this embodiment tends to show continuous changes in a wide temperature range and has excellent tensile strength.
  • the glass transition temperature of the conjugated diene polymer of the present embodiment can be calculated using the Gordon-Taylor equation (Gordon, M.; Taylor, J. S. J. Appl. Chem. 1952, 2, 493.) expanded to a system of two or more components of the following formula (1). The value calculated by this method is called the estimated glass transition temperature (estimated Tg).
  • the subscript i of the variable represents each component of the microstructure contained in the conjugated diene polymer
  • ⁇ i is the difference in thermal expansion coefficient before and after the glass transition of the homopolymer of the i component
  • w i is the mass ratio of the i component in the conjugated diene polymer
  • Tg i is the glass transition temperature of the homopolymer of the i component
  • ⁇ i is the density of the homopolymer of the i component. All of these can be used as literature values or measured values.
  • ⁇ i 3.6 ⁇ 10 -4 K -1
  • Tg i 105.3 ° C. based on the measured value of the glass transition temperature
  • ⁇ i 1.02 g / cm 3 based on the measured value of the density.
  • the estimated glass transition temperature (estimated Tg) can be calculated from the following formula (i) using the bound aromatic vinyl monomer unit amount X all (mass %), the vinyl bond amount Y all (mol %) in the bound conjugated diene, and the thermal expansion coefficients ( ⁇ a i ), glass transition temperatures (Tg i ), and densities ( ⁇ i ) of polystyrene (PS), poly-1,2-butadiene (1,2-PBd), and poly-1,4-butadiene (1,4-PBd).
  • conjugated diene polymers in the case of butadiene homopolymers and butadiene-styrene copolymers, the physical properties of conjugated diene polymers can be predicted by the above formula (iii) from the values normally used in design.
  • the mass ratio of each microstructure component can be calculated from the microstructure such as the bound aromatic vinyl monomer unit amount Xall (mass%) in the conjugated diene polymer of this embodiment and the vinyl bond amount Yall (mol%) in the bound conjugated diene, and the glass transition temperature (Tg) of the conjugated diene polymer can be estimated. That is, the estimated Tg is a measure representing the change in the glass transition temperature of the conjugated diene polymer with respect to the change in the bound aromatic vinyl monomer unit amount Xall (mass%) and the vinyl bond amount Yall (mol%) in the bound conjugated diene.
  • the glass transition temperature (Tg) of the conjugated diene polymer of this embodiment is small, and when the estimated Tg value is large, the glass transition temperature (Tg) of the conjugated diene polymer of this embodiment is high.
  • the glass transition temperature of the conjugated diene polymer is estimated to be -70°C
  • the glass transition temperature of the conjugated diene polymer is estimated to be -45°C.
  • the estimated Tg value obtained from the microstructure of a conjugated diene polymer is generally an index of the glass transition temperature of the conjugated diene polymer, but the present inventors have found that when the relaxation of the conjugated diene polymer near the actual glass transition temperature is over a wide range of temperatures, the actual viscoelasticity of the vulcanizate does not necessarily match the viscoelasticity based on the estimated glass transition temperature calculated from the microstructure.
  • the mismatch between the glass transition temperature (estimated Tg) estimated from the above formula (1) and the actually measured glass transition temperature (Tg) tends to become significant. Therefore, from the viewpoint of controlling the performance of a vulcanizate that is affected by the glass transition temperature, it has been found that it is more effective to control the estimated Tg value calculated from the microstructure to a specific value than to control the actually measured glass transition temperature of the conjugated diene polymer to a specific value.
  • DSC differential scanning calorimetry
  • the conjugated diene polymer of this embodiment has an estimated Tg that falls within the range of -72°C or more and -45°C or less, so that the measured glass transition temperature when vulcanized becomes an optimal value, and tends to have an excellent balance between wet grip performance and low temperature performance.
  • the conjugated diene polymer of the present embodiment has a lower limit of the estimated Tg derived from the microstructure of ⁇ 72° C. or higher, preferably ⁇ 70° C. or higher, and more preferably ⁇ 68° C. or higher.
  • the upper limit of the estimated Tg value is ⁇ 45° C. or less, preferably ⁇ 48° C. or less, and more preferably ⁇ 50° C. or less.
  • the upper limit of the estimated Tg is within the above range, the low-temperature performance of the vulcanizate of the conjugated diene polymer of the present embodiment tends to be improved.
  • the estimated Tg can be controlled to the above-mentioned numerical range by adjusting the microstructure of the conjugated diene polymer.
  • the conjugated diene polymer of the present embodiment is a butadiene-styrene copolymer
  • the estimated Tg can be controlled to the above-mentioned numerical range by adjusting the bound styrene amount X all (mass %) of the conjugated diene polymer and the vinyl bond amount Y all (mol %) in the bound butadiene according to the above formula (iii).
  • the conjugated diene-based polymer of the present embodiment preferably has two or more polymer segments.
  • the polymer segment refers to a portion of a conjugated diene-based polymer that is composed of conjugated diene monomer units and aromatic vinyl monomer units, or that is composed of conjugated diene monomer units.
  • the conjugated diene polymer of the present embodiment preferably has a small number or no blocks in which 4 or more linked aromatic vinyl monomer units are chained in the polymer segment.
  • the Tg width tends to be wide, which is preferable from the viewpoint of increasing the difference between the extrapolated glass transition onset temperature and the extrapolated glass transition end temperature, but the glass transition temperature measured by DSC tends to be easily divided into two.
  • the multiple polymer segments contained in the conjugated diene polymer of this embodiment have different microstructures. Each polymer segment may have a different amount of bound aromatic vinyl monomer units or a different amount of vinyl bonds in the bound conjugated diene. Each polymer segment can be distinguished by the method described in the examples below.
  • the conjugated diene polymer of the present embodiment preferably has a first polymer segment that does not contain an aromatic vinyl monomer unit and a second polymer segment that contains an aromatic vinyl monomer unit. This makes the estimated Tg value of the first polymer segment smaller than the estimated Tg value of the conjugated diene polymer of the present embodiment (the value of formula (1) of the entire polymer). In this case, the estimated Tg of the first polymer segment is calculated by applying each component of the microstructure of the conjugated diene polymer to the above formula (1).
  • the estimated Tg of the conjugated diene polymer is calculated from the bound styrene amount X all (mass %) of the conjugated diene polymer and the vinyl bond amount Y all (mol %) in the bound butadiene according to the above formula (iii).
  • the first polymer segment does not contain an aromatic vinyl monomer unit, and the vinyl bond amount Y 1 (mol %) in the bonded conjugated diene satisfies the following formula (2). 10 ⁇ Y 1 ⁇ 45...(2)
  • the lower limit of Y1 is more preferably greater than 10, even more preferably 12 or more, and even more preferably 15 or more.
  • the upper limit of Y1 is more preferably less than 45, even more preferably 43 or less, and even more preferably 40 or less.
  • the vinyl bond amount Y 1 (mol %) in the bound conjugated diene can be controlled within the above numerical range by adjusting the amount of polar substance added in the first polymerization step for preparing the first polymer segment.
  • the conjugated diene-based polymer of the present embodiment preferably has a first polymer segment not containing an aromatic vinyl monomer unit and a second polymer segment containing an aromatic vinyl monomer unit.
  • the second polymer segment has an estimated Tg value larger than that of the conjugated diene polymer of this embodiment.
  • the estimated Tg of the second polymer segment is calculated by applying each component of the microstructure of the second polymer segment to the above formula (1).
  • the estimated Tg of the conjugated diene polymer is calculated from the bound styrene amount X all (mass %) of the conjugated diene polymer and the vinyl bond amount Y all (mol %) in the bound butadiene according to the above formula (iii).
  • the second polymer segment preferably has an estimated Tg of higher than ⁇ 45° C. and equal to or lower than ⁇ 5° C.
  • the estimated Tg of the second polymer segment can be calculated from the microstructure such as the amount of bound aromatic vinyl monomer units X all (mass %) of the second polymer segment and the amount of vinyl bonds Y all (mol %) in the bound conjugated diene, according to the above formula (1).
  • the lower limit of the estimated Tg of the second polymer segment is preferably higher than -45°C, more preferably -44°C or higher, and further preferably -43°C or higher.
  • the upper limit of the estimated Tg of the second polymer segment is preferably ⁇ 5° C. or lower, more preferably ⁇ 10° C. or lower, and further preferably ⁇ 15° C. or lower.
  • the estimated Tg of the second polymer segment of the conjugated diene polymer of this embodiment can be controlled to the above-mentioned numerical range by adjusting the microstructure of the second polymer segment.
  • the conjugated diene-based polymer of the present embodiment may contain a polymer segment other than the first polymer segment and the second polymer segment.
  • the conjugated diene-based polymer may contain a third polymer segment made of a conjugated diene compound in order to increase the reactivity of the conjugated diene-based polymer with a coupling agent.
  • the polymer segments may be bonded to each other directly or via a coupling agent.
  • the polymer segment ratio in a conjugated diene polymer refers to the average mass fraction of each polymer segment relative to the entire conjugated diene polymer.
  • the first and second polymer segment ratios are defined as the ratio of the mass of the polymer segments obtained in the first polymerization step (P1), which is a step for preparing the first polymer segment, and the second polymerization step (P2), which is a step for forming the second polymer segment, to the total mass of the conjugated diene-based polymer.
  • the segment ratio (r 1 ) of the first polymer segment is preferably 20 mass% or more and 80 mass% or less, more preferably 30 mass% or more and 70 mass% or less, and even more preferably 40 mass% or more and 60 mass% or less.
  • the ratio of the first polymer segment in the conjugated diene polymer of this embodiment falls within a preferred range, and the flexibility of the conjugated diene polymer in the low temperature range when vulcanized is improved, and the vulcanized product tends to have excellent wear resistance.
  • the second polymer segment ratio ( r2 ) in the conjugated diene polymer falls within a preferred range, and the wet grip performance tends to be excellent.
  • the segment ratio (r 1 ) of the first polymer segment in the conjugated diene polymer of this embodiment can be controlled within the above numerical range by adjusting the polymerization conditions, such as the amount of monomer added and polymerization time, in the first polymerization step (P1).
  • the method for introducing multiple polymer segments into the molecule of the conjugated diene polymer of this embodiment is not particularly limited, but an example is a method in which a continuous solution polymerization method is used in which multiple reactors are arranged in series, as described below, and a conjugated diene compound, an aromatic vinyl compound, a polar substance, and a solvent are added sequentially to each reactor.
  • the substances added sequentially may be the same or different between the reactors.
  • the conjugated diene polymer of this embodiment has only one glass transition temperature (Tg) measured by differential scanning calorimetry (DSC), and the difference between the extrapolated glass transition onset temperature and the extrapolated glass transition end temperature of the glass transition temperature (Tg) is from 15° C. to 35° C.
  • One conjugated diene polymer undergoes glass transition in a wide temperature range, that is, has a region in which it relaxes from an elastic body to a viscous body in a wide temperature range, so that the vulcanizate thereof is easily made viscous in a low temperature range and has excellent low-temperature performance, and in addition, the elastic region of the vulcanizate thereof continues even in a high temperature range and has excellent wet grip performance, resulting in an excellent balance between both properties.
  • the conjugated diene polymer of the present embodiment has only one glass transition temperature (Tg) as measured by DSC.
  • Tg glass transition temperature
  • aromatic vinyl monomer unit bonds are contained only in 30 mass% from the end of a conjugated diene polymer, and 40 mass% of that is aromatic vinyl monomer units
  • the conjugated diene polymer has two glass transition temperatures. Having one glass transition temperature (Tg) means that the conjugated diene polymer is not phase-separated, and tends to exhibit good low-temperature properties when vulcanized.
  • the glass transition temperature (Tg) of the conjugated diene polymer of this embodiment indicates a temperature near the middle between the extrapolated glass transition onset temperature and the extrapolated glass transition end temperature of differential scanning calorimetry (DSC).
  • the measured Tg value is preferably -75°C or higher, more preferably -70°C or higher.
  • the glass transition temperature (Tg) of the conjugated diene polymer of this embodiment is preferably -45°C or lower, more preferably -50°C or lower.
  • the glass transition temperature (Tg) may be within a range that arbitrarily combines the above upper and lower limits.
  • the glass transition temperature (Tg) of the conjugated diene polymer of this embodiment is measured in accordance with ISO 22768:2006.
  • a DSC curve is recorded by performing differential scanning calorimetry (DSC) measurement while increasing the temperature within a predetermined temperature range, and the inflection point of the DSC curve is taken as the glass transition temperature. Specifically, it can be measured by the method described in the examples described below.
  • the conjugated diene polymer of the present embodiment may contain plasticizing components such as resins and process oils described below. However, these components must be removed in the DSC measurement for determining the Tg of the conjugated diene polymer of the present embodiment.
  • the glass transition temperature (Tg) of a conjugated diene polymer varies depending on the amount of bound aromatic vinyl monomer units in the conjugated diene polymer and the amount of vinyl bonds in the bound conjugated diene. Specifically, the glass transition temperature (Tg) increases when the amount of bound aromatic vinyl monomer units and the amount of vinyl bonds in the bound conjugated diene are increased, whereas the glass transition temperature (Tg) decreases when the amount of bound aromatic vinyl monomer units and the amount of vinyl bonds in the bound conjugated diene are decreased.
  • the above-mentioned estimated Tg can be controlled to a suitable numerical range by adjusting the microstructure, whereby the actually measured glass transition temperature (Tg) can be controlled to a preferred range.
  • the extrapolated glass transition onset temperature of the glass transition temperature (Tg) of the conjugated diene polymer of this embodiment is preferably -90°C or higher, more preferably -85°C or higher.
  • the extrapolated glass transition onset temperature is preferably -60°C or lower, more preferably -65°C or lower.
  • the extrapolated glass transition end temperature of the glass transition temperature (Tg) of the conjugated diene polymer of this embodiment is preferably -70°C or higher, more preferably -65°C or higher.
  • the extrapolated glass transition end temperature is preferably -40°C or lower, more preferably -45°C or lower.
  • the vulcanizate of the conjugated diene polymer of this embodiment tends to have even better low hysteresis loss properties.
  • the conjugated diene polymer of the present embodiment has only one glass transition temperature (Tg) as measured by DSC, and the difference between the extrapolated glass transition onset temperature and the extrapolated glass transition end temperature of the glass transition temperature is from 15° C. to 30° C.
  • Tg glass transition temperature
  • the conjugated diene polymer of this embodiment is a conjugated diene polymer having, for only one glass transition temperature, a difference between the extrapolated glass transition onset temperature and the extrapolated glass transition end temperature of 15° C. or more.
  • the lower limit of the difference between the extrapolated glass transition onset temperature and the extrapolated glass transition end temperature is preferably 15.5° C. or more, more preferably 18° C. or more.
  • the upper limit is preferably 35° C. or less, more preferably 30° C. or less.
  • the extrapolated glass transition onset temperature varies depending on the amount of vinyl bonds Y1 in the bound conjugated diene of the first polymer segment. Specifically, the extrapolated glass transition onset temperature increases with an increase in the amount of vinyl bonds Y1 in the bound conjugated diene. On the other hand, the extrapolated glass transition onset temperature decreases with a decrease in the amount of bound aromatic vinyl monomer units X1 of the first polymer segment and a decrease in the amount of vinyl bonds Y1 in the bound conjugated diene. For example, when Y1 is 20 (mol %), the extrapolated glass transition onset temperature is -76.5°C, whereas when Y1 is 15 (mol %), the extrapolated glass transition onset temperature is -78.0°C.
  • the extrapolated glass transition end temperature varies depending on the amount of bound aromatic vinyl monomer units X2 of the second polymer segment, the amount of vinyl bonds Y2 in the bound conjugated diene, and the second polymer segment ratio r2 . Specifically, the extrapolated glass transition end temperature increases with an increase in the amount of bound aromatic vinyl monomer units X2 and the amount of vinyl bonds Y2 in the bound conjugated diene or an increase in the second polymer segment ratio r2 . On the other hand, the extrapolated glass transition end temperature decreases with a decrease in the amount of bound aromatic vinyl monomer units X2 and the amount of vinyl bonds Y2 in the bound conjugated diene or a decrease in the second polymer segment ratio r2 .
  • the extrapolated glass transition end temperature is ⁇ 53.0° C.
  • the extrapolated glass transition onset temperature is ⁇ 58.0° C.
  • the extrapolated glass transition end temperature is -46.0°C.
  • the weight average molecular weight (Mw) of the conjugated diene polymer of the present embodiment measured by GPC measurement is preferably 27 ⁇ 10 4 or more, more preferably 30 ⁇ 10 4 or more, even more preferably 40 ⁇ 10 4 or more, and still more preferably 45 ⁇ 10 4 or more.
  • the weight average molecular weight is preferably not more than 135 ⁇ 10 4 , more preferably not more than 90 ⁇ 10 4 , and even more preferably not more than 70 ⁇ 10 4.
  • the weight average molecular weight may be within a range that is any combination of the upper and lower limits described above.
  • the weight average molecular weight of the conjugated diene polymer can be measured by a GPC measurement method, specifically, by the method described in the examples described later.
  • the number average molecular weight of the conjugated diene polymer of the present embodiment measured by the GPC measurement method is preferably 17 x 10 4 or more, more preferably 19 x 10 4 or more, and even more preferably 23 x 10 4 or more.
  • the vulcanizate tends to have excellent abrasion resistance.
  • the number average molecular weight is preferably 80 x 10 4 or less, more preferably 50 x 10 4 or less, and even more preferably 40 x 10 4 or less.
  • the number average molecular weight may be within a range that arbitrarily combines the upper limit and the lower limit.
  • the number average molecular weight of the conjugated diene polymer can be measured by the GPC measurement method, specifically, it can be measured by the method described in the examples described later.
  • the weight-average molecular weight and number-average molecular weight of the conjugated diene polymer can be controlled within the above numerical range by adjusting the ratio of the amount of polymerization initiator used to the amount of monomer used, and the type and amount of coupling agent used.
  • the molecular weight distribution of the conjugated diene polymer of this embodiment is represented by the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn).
  • the conjugated diene polymer of this embodiment preferably has a molecular weight distribution of 1.7 to 2.5.
  • a conjugated diene polymer having a molecular weight distribution in this range tends to have better processability when made into a vulcanizate.
  • the molecular weight distribution of the conjugated diene polymer of the present embodiment is more preferably 1.75 or more, and even more preferably 1.8 or more.
  • the molecular weight distribution is more preferably 2.4 or less, and even more preferably 2.2 or less.
  • the Mooney viscosity of the modified conjugated diene polymer of this embodiment measured at 100°C is preferably 30 or more and 150 or less, more preferably 60 or more and 130 or less, and even more preferably 60 or more and 115 or less.
  • the Mooney viscosity of the conjugated diene polymer of this embodiment can be measured by the method described in the examples below.
  • the conjugated diene polymer of the present embodiment preferably has a nitrogen atom, and more specifically, preferably has a modifying group having a nitrogen atom.
  • the "modification rate” refers to the content, expressed in mass %, of a conjugated diene polymer component having a specific functional group in the polymer molecule that has affinity or binding reactivity with a filler relative to the total amount of the conjugated diene polymer mixture when a conjugated diene polymer is modified with a modifying agent having a nitrogen atom to obtain a mixture of modified and unmodified conjugated diene polymers. Therefore, when the specific functional group contains a nitrogen atom, the "modification rate” refers to the mass ratio of the nitrogen-atom-containing conjugated diene polymer relative to the total amount of the conjugated diene polymer mixture.
  • the modification rate is the mass ratio of the conjugated diene polymer having a nitrogen atom-containing functional group resulting from the nitrogen atom-containing modifying agent to the total amount of the conjugated diene polymer.
  • the degree of modification can be measured by chromatography, which is capable of separating the functional group-containing modified and unmodified components.
  • chromatography is capable of separating the functional group-containing modified and unmodified components.
  • methods using chromatography include a method in which a gel permeation chromatography column is packed with a polar substance such as silica that adsorbs specific functional groups, and the non-adsorbed components are quantified using an internal standard for comparison.
  • the modification rate is obtained by measuring the amount of adsorption to the silica column from the difference between a chromatogram obtained by measuring a sample solution containing a sample and a low-molecular-weight internal standard polystyrene using a polystyrene-based gel column and a chromatogram obtained by measuring a sample solution using a silica-based column. More specifically, the modification rate can be measured by the method described in the Examples.
  • the modification rate can be controlled by adjusting the amount of the modifier added and the reaction method.
  • a desired modification rate can be achieved by combining a method of polymerization using an organolithium compound having at least one nitrogen atom in the molecule described below as a polymerization initiator, a method of copolymerizing a monomer having at least one nitrogen atom in the molecule, and a method of using a modifying agent having a structural formula described below, and controlling the polymerization conditions.
  • the conjugated diene polymer of this embodiment preferably has a modification rate of 60% or more, more preferably 65% or more, and even more preferably 70% or more, based on the total amount of the conjugated diene polymer.
  • the method for producing the conjugated diene polymer of the present embodiment is not limited to the following:
  • the method may include a method using two or more continuous reactors, which includes a first polymerization step (P1) in which a conjugated diene compound, a polymerization initiator, and a polar substance are added to the continuous reactors to continuously form a first polymer segment of a conjugated diene-based polymer, and a second polymerization step (P2) in which an aromatic vinyl compound and a polar substance are added to the continuous reactors to form a second polymer segment at an end of the first polymer segment.
  • the continuous reactor preferably has two or more reactors.
  • the polymerization initiator As the polymerization initiator, at least an organic monolithium compound can be used.
  • the organomonolithium compound is not limited to the following, but examples thereof include low molecular weight compounds and solubilized oligomeric organomonolithium compounds.
  • examples of the organomonolithium compound include compounds having a carbon-lithium bond, a nitrogen-lithium bond, and a tin-lithium bond in terms of the bonding mode between the organic group and the lithium.
  • the amount of the organic monolithium compound used as the polymerization initiator is preferably determined depending on the molecular weight of the target conjugated diene polymer or modified conjugated diene polymer.
  • the amount of a monomer such as a conjugated diene compound used relative to the amount of a polymerization initiator used is related to the degree of polymerization, that is, tends to be related to the number average molecular weight and the weight average molecular weight. Therefore, in order to increase the molecular weight, the amount of the polymerization initiator used should be adjusted to decrease, and in order to decrease the molecular weight, the amount of the polymerization initiator used should be adjusted to increase.
  • the organomonolithium compound is preferably an alkyllithium compound having a substituted amino group or a dialkylaminolithium, from the viewpoint that the organomonolithium compound is used as one method for introducing nitrogen atoms into a conjugated diene-based polymer.
  • a conjugated diene polymer having a nitrogen atom consisting of an amino group at the polymerization initiation terminal is obtained.
  • the substituted amino group is an amino group that does not have an active hydrogen or has a structure in which the active hydrogen is protected.
  • alkyllithium compounds having an amino group that does not have an active hydrogen include, but are not limited to, 3-dimethylaminopropyllithium, 3-diethylaminopropyllithium, 4-(methylpropylamino)butyllithium, and 4-hexamethyleneiminobutyllithium.
  • alkyllithium compounds having an amino group with an active hydrogen protected structure include, but are not limited to, 3-bistrimethylsilylaminopropyllithium and 4-trimethylsilylmethylaminobutyllithium.
  • dialkylaminolithium examples include, but are not limited to, lithium dimethylamide, lithium diethylamide, lithium dipropylamide, lithium dibutylamide, lithium di-n-hexylamide, lithium diheptylamide, lithium diisopropylamide, lithium dioctylamide, lithium-di-2-ethylhexylamide, lithium didecylamide, lithium ethylpropylamide, lithium ethylbutylamide, lithium ethylbenzylamide, lithium methylphenethylamide, lithium hexamethylene imide, lithium pyrrolidide, lithium piperidide, lithium heptamethylene imide, lithium morpholide, 1-lithioazacyclooctane, 6-lithio-1,3,3-trimethyl-6-azabicyclo[3.2.1]octane, and 1-lithio-1,2,3,6-tetrahydropyridine.
  • organomonolithium compounds having a substituted amino group can also be used as solubilized oligomeric organomonolithium compounds by reacting them with a small amount of a polymerizable monomer, such as 1,3-butadiene, isoprene, or styrene.
  • a polymerizable monomer such as 1,3-butadiene, isoprene, or styrene.
  • the polymerization initiator may be one produced by reacting an aromatic vinyl compound and/or a conjugated diene compound having a substituted amino group with an organic monolithium compound, or may be one capable of introducing a functional group into one end of a polymer chain.
  • the organomonolithium compound is preferably an alkyllithium compound from the viewpoints of industrial availability and ease of control of the polymerization reaction, in which case a conjugated diene-based polymer having an alkyl group at the polymerization initiation terminal can be obtained.
  • alkyl lithium compound examples include, but are not limited to, n-butyl lithium, sec-butyl lithium, tert-butyl lithium, n-hexyl lithium, benzyl lithium, phenyl lithium, and stilbene lithium.
  • alkyllithium compound n-butyllithium and sec-butyllithium are preferred from the viewpoints of industrial availability and ease of control of the polymerization reaction.
  • organomonolithium compounds may be used alone or in combination of two or more kinds, and may also be used in combination with other organometallic compounds.
  • the other organometallic compounds include alkaline earth metal compounds, other alkali metal compounds, and other organometallic compounds.
  • Alkaline earth metal compounds include, but are not limited to, organomagnesium compounds, organocalcium compounds, and organostrontium compounds, as well as alkaline earth metal alkoxides, sulfonates, carbonates, and amides.
  • organomagnesium compounds include dibutylmagnesium and ethylbutylmagnesium.
  • Other organometallic compounds include organoaluminum compounds.
  • a coupling step (P3) of reacting the conjugated diene polymer with a coupling agent may be carried out after the second polymerization step (P2).
  • the weight average molecular weight of the conjugated diene polymer before the coupling step (P3) can be controlled by adjusting the amount of polymerization initiator used relative to the conjugated diene compound and aromatic vinyl compound, and the weight average molecular weight tends to decrease as the amount of polymerization initiator used decreases.
  • the amount of polymerization initiator used is preferably 0.15 mol or more and 1.5 mol or less, assuming that the total mass of the conjugated diene compound and aromatic vinyl compound used is 100 kg.
  • a polar substance may be added.
  • the aromatic vinyl compound can be randomly copolymerized with the conjugated diene compound by the polar substance, and the polar substance tends to be usable as a vinylizing agent for controlling the microstructure of the conjugated diene portion.
  • the polar substance tends to be effective in promoting the polymerization reaction.
  • polar substances include, but are not limited to, ethers such as tetrahydrofuran, diethyl ether, dioxane, ethylene glycol dimethyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol dibutyl ether, dimethoxybenzene, and 2,2-bis(2-oxolanyl)propane; tertiary amine compounds such as tetramethylethylenediamine, dipiperidinoethane, trimethylamine, triethylamine, pyridine, and quinuclidine; alkali metal alkoxide compounds such as potassium tert-amylate, potassium tert-butylate, sodium tert-butylate, and sodium amylate; and phosphine compounds such as triphenylphosphine.
  • ethers such as tetrahydrofuran, diethyl ether, dioxane, ethylene glycol dimethyl ether
  • polar substances may be used alone or in combination of two or more.
  • the amount of the polar substance used is not particularly limited and can be selected depending on the purpose, but is preferably 0.01 moles or more and 100 moles or less per mole of the polymerization initiator.
  • Such polar substances can be used in appropriate amounts according to the desired vinyl bond amount as regulators for the microstructure of the conjugated diene portion of the conjugated diene polymer.
  • Many polar substances simultaneously exert an effective randomizing effect in the copolymerization of a conjugated diene compound and an aromatic vinyl compound, and tend to be able to adjust the randomness of the aromatic vinyl monomer units and the conjugated diene monomer units of each polymer segment.
  • a copolymerization reaction may be started with the whole amount of styrene and a part of 1,3-butadiene, and the remaining 1,3-butadiene may be intermittently added during the copolymerization reaction.
  • the 1,3-butadiene added here is added in order to obtain a high modification rate in the coupling step (P3), and does not necessarily have to form a polymer segment.
  • the polymerization temperature in the polymerization step is preferably a temperature at which living anionic polymerization proceeds, and from the viewpoint of productivity, is preferably 0°C or higher, and more preferably 120°C or lower. By being in this range, it tends to be possible to ensure a sufficient amount of modifier reacting with the active terminals after polymerization is completed. Even more preferably, it is 50°C or higher and 100°C or lower.
  • the polymerization step is carried out in a continuous reactor system using two or more continuous reactors, and as described above, a first polymerization step (P1) for obtaining a first polymer segment and a second polymerization step (P2) for obtaining a second polymer segment are carried out.
  • the first polymerization step (P1) and the second polymerization step (P2) can each be carried out using one or two or more connected reactors.
  • the shape of the reactor may be any shape, such as a tank type with a stirrer or a tube type.
  • first polymerization step (P1) and the second polymerization step (P2) are assigned to each reactor, and for example, the second polymerization step (P2) may be set to start downstream of the first reactor.
  • Each reactor may have a temperature control function.
  • a continuous reactor system one or more connected reactors can be used.
  • the continuous reactor may be, for example, a tank type or a tubular type equipped with an agitator.
  • the monomer, the inert solvent, and the polymerization initiator are continuously fed to the reactor, a polymer solution containing a conjugated diene polymer is obtained in the reactor, and the conjugated diene polymer solution is continuously discharged.
  • a continuous system is preferred to obtain a conjugated diene polymer, which allows the polymer to be continuously discharged and subjected to the next reaction in a short time.
  • a reaction system in which continuous tank reactors are connected in series is used, which increases the residence time distribution in the reactor and the molecular weight distribution of each polymer segment.
  • the randomization effect of the aromatic vinyl compound increases. This suppresses microphase separation of the conjugated diene polymer when vulcanized, resulting in a single glass transition temperature, and also tends to result in excellent wet grip performance and low temperature performance.
  • a conjugated diene compound, a polymerization initiator, and a polar substance are added to a reactor and polymerization is carried out continuously.
  • the conjugated diene polymer solution after the first polymerization step (P1) is continuously distilled from the reactor and sent to the next step.
  • the liquid destination is preferably, for example, the second polymerization step (P2) for forming the second polymer segment.
  • the second polymerization step (P2) for the second polymer segment one or more connected reactors are used similarly to the polymerization step (P1).
  • An aromatic vinyl compound and an additional polar substance are added to the conjugated diene-based polymer of the first polymer segment obtained in the first polymerization step (P1) to continuously polymerize the polymer.
  • the conjugated diene polymer solution after the second polymerization step (P2) is continuously distilled from the reactor and sent to the next step.
  • the destination of the solution is preferably, for example, the coupling step (P3) described below.
  • the conjugated diene polymer of the present embodiment can also be produced by the following method. That is, in order to form a first polymer segment and a second polymer segment in a conjugated diene-based polymer, it is also possible to use a continuous polymerization method for two or more groups, for example, by adding an aromatic vinyl compound, a conjugated diene compound, a polymerization initiator, and a polar substance to a first reactor in a first polymerization step (P1) for producing a first polymer segment and continuously polymerizing the same, while changing the conditions of the polymerization steps in the respective reactors in a second polymerization step (P2) for forming a second polymer segment without adding an additional aromatic vinyl compound to the second reactor and any subsequent reactors, thereby producing the conjugated diene-based polymer of the present embodiment.
  • P1 first polymerization step
  • P2 second polymerization step
  • the polymerization reaction rate in the first reactor in the first polymerization step (P1) is reduced, and the conjugated diene compound and aromatic vinyl compound unreacted in the first polymerization step (P1) are polymerized in the second polymerization step (P2) or later, thereby making it possible to form a first polymer segment and a second polymer segment in the conjugated diene polymer.
  • the above-mentioned production method becomes easy.
  • the molecular weight distribution of the conjugated diene polymer is decreased.
  • the processability of the vulcanizate thereof tends to be excellent.
  • the polymerization reaction rate in the first polymerization step (P1) is preferably 75% or more and 95% or less. More preferably, it is 80% or more and 94% or less, and even more preferably, it is 85% or more and 93% or less.
  • the mass ratio of the conjugated diene compound added in the first polymerization step (P1) to the total amount of the conjugated diene compound and the aromatic vinyl compound added is preferably 20 mass% or more and 80 mass% or less, more preferably 30 mass% or more and 70 mass% or less, and even more preferably 40 mass% or more and 60 mass% or less.
  • the ratio of the first polymer segment to the conjugated diene-based polymer can be preferably 20% by mass or more and 80% by mass or less, more preferably 30% by mass or more and 70% by mass or less, and even more preferably 40% by mass or more and 60% by mass or less.
  • the polymerization reaction rate in the first polymerization step (P1) can be calculated using the following formula (7).
  • the polymerization reaction rate in the first polymerization step (P1) can be calculated from the solid amount of the conjugated diene-based polymer per hour after the first polymerization step (P1) relative to the total amount of the conjugated diene compound and the aromatic vinyl compound added per hour in the first polymerization step (P1).
  • the amount of solids (m1) in the conjugated diene polymer solution is determined from the amount of non-volatile components in the polymer solution flowing from the outlet of the first polymerization step (P1) per unit time.
  • the entire amount of the polymer solution flowing through the outlet of the first polymerization step (P1) is collected for 3 minutes, and a polymerization terminator is immediately added.
  • the solution is then transferred to a heat-resistant dish or the like, and dried in a 140°C oven for 30 minutes or more, and the mass M1 of the remaining solid matter is measured.
  • the solid amount (m1) is calculated by combining the following formulas (7) and (8).
  • the second polymerization step (P2) for forming the second polymer segment it is preferable to add an aromatic vinyl compound as described above.
  • the mass ratio of the amount of the aromatic vinyl compound to the amount of the conjugated diene compound added in the second polymerization step (P2) the proportion of the aromatic vinyl monomer unit in the second polymer segment can be controlled, which tends to make it possible to maintain the elastic properties of the conjugated diene polymer in the high temperature range.
  • the lower limit of the mass ratio is preferably 0.15 or more, more preferably 0.25 or more, and even more preferably 0.30 or more.
  • the upper limit of the mass ratio of the amount of the aromatic vinyl compound added to the amount of the conjugated diene compound added in the second polymerization step (P2) is preferably 0.70 or less, more preferably 0.65 or less, and even more preferably 0.60 or less.
  • the amount of the aromatic vinyl compound added in the second polymerization step (P2) By adjusting the amount of the aromatic vinyl compound added in the second polymerization step (P2) to fall within a predetermined range, the amount of bound aromatic vinyl monomer units in the second polymer segment in the conjugated diene polymer can be adjusted to fall within a desired range, and the vulcanizate tends to have excellent handling stability.
  • one or more polar substances may be added, which increases the vinyl bond amount Y2 in the bonded conjugated diene of the second polymer segment and tends to improve the wet grip performance of the vulcanizate.
  • the amount of polar substance added in the second polymerization step (P2) is not particularly limited and can be selected according to the purpose, but is preferably 0.01 moles or more and 100 moles or less per mole of polymerization initiator, including the polar substance added in the first polymerization step (P1).
  • the amount of polar substance added in the second polymerization step (P2) is greater than that in the first polymerization step (P1).
  • it is preferably more than 1.0 times and 25 times or less, and more preferably 1.5 times or more and 20 times or less.
  • a predetermined process may be included before and after the first polymerization process (P1) and before and after the second polymerization process (P2).
  • a polymerization process may be provided to form a polymer segment different from the first polymer segment and the second polymer segment.
  • the polymerization steps are preferably carried out in the order of the first polymerization step (P1) and the second polymerization step (P2), but are not limited thereto.
  • the first polymerization step (P1) is carried out at a high polymerization temperature without adding an aromatic vinyl compound, thereby producing a modified conjugated diene-based polymer in which the coupling step is carried out after the second polymer segment and the first polymer segment.
  • the conversion rate is high in each polymerization step.
  • a coupling agent for example, a reactive compound having three or more functionalities
  • a step of modifying the active terminal of the conjugated diene polymer using a modifying agent having a nitrogen atom-containing group preferably a coupling agent having a nitrogen atom-containing group.
  • the step of performing coupling and/or modification will be referred to as the coupling step (P3).
  • the coupling step (P3) one of the active terminals of the conjugated diene polymer is modified with a coupling agent or a modifying agent having a nitrogen atom to obtain a modified conjugated die
  • the coupling agent used in the coupling step may have any structure as long as it is a reactive compound having three or more functionalities, but is preferably a reactive compound having three or more functionalities and a silicon atom.
  • trifunctional or higher reactive compounds having silicon atoms include, but are not limited to, halogenated silane compounds, epoxy silane compounds, vinylated silane compounds, alkoxy silane compounds, and alkoxy silane compounds containing nitrogen-containing groups, with amino alkoxy silane compounds being preferred.
  • Halogenated silane compounds that serve as coupling agents include, but are not limited to, methyltrichlorosilane, tetrachlorosilane, tris(trimethylsiloxy)chlorosilane, tris(dimethylamino)chlorosilane, hexachlorodisilane, bis(trichlorosilyl)methane, 1,2-bis(trichlorosilyl)ethane, 1,2-bis(methyldichlorosilyl)ethane, 1,4-bis(trichlorosilyl)butane, 1,4 bis(methyldichlorosilyl)butane, etc.
  • Epoxy silane compounds that are coupling agents include, but are not limited to, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, epoxy-modified silicone, etc.
  • the nitrogen atom-containing modifying agent include, but are not limited to, isocyanate compounds, isothiocyanate compounds, isocyanuric acid derivatives, nitrogen atom group-containing carbonyl compounds, nitrogen atom group-containing vinyl compounds, and nitrogen atom group-containing epoxy compounds.
  • Isocyanate compounds that are modifying agents having nitrogen atom-containing groups include, but are not limited to, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, diphenylmethane diisocyanate, polymeric diphenylmethane diisocyanate (C-MDI), phenyl isocyanate, isophorone diisocyanate, hexamethylene diisocyanate, butyl isocyanate, 1,3,5-benzene triisocyanate, etc.
  • Isocyanuric acid derivatives which are modifying agents having a nitrogen atom-containing group, include, but are not limited to, 1,3,5-tris(3-trimethoxysilylpropyl)isocyanurate, 1,3,5-tris(3-triethoxysilylpropyl)isocyanurate, 1,3,5-tri(oxiran-2-yl)-1,3,5-triazinane-2,4,6-trione, 1,3,5-tris(isocyanatomethyl)-1,3,5-triazinane-2,4,6-trione, 1,3,5-trivinyl-1,3,5-triazinane-2,4,6-trione, etc.
  • Carbonyl compounds that are modifiers having a nitrogen atom-containing group include, but are not limited to, 1,3-dimethyl-2-imidazolidinone, 1-methyl-3-ethyl-2-imidazolidinone, 1-methyl-3-(2-methoxyethyl)-2-imidazolidinone, N-methyl-2-pyrrolidone, N-methyl-2-piperidone, N-methyl-2-quinolone, 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(dimethylamino)benzophenone, methyl
  • Examples of such compounds include methyl-2-pyridyl ketone, methyl-4-pyridyl ketone, propyl-2-pyridyl ketone, di-4-pyridyl ketone, 2-benzoylpyridine, N,N,N',N'-tetramethylurea, N,N-dimethyl-N',N'-diphenylurea, N,
  • Vinyl compounds that are modifiers having nitrogen atom-containing groups include, but are not limited to, N,N-dimethylacrylamide, N,N-dimethylmethacrylamide, N-methylmaleimide, N-methylphthalimide, N,N-bistrimethylsilylacrylamide, morpholinoacrylamide, 3-(2-dimethylaminoethyl)styrene, (dimethylamino)dimethyl-4-vinylphenylsilane, 4,4'-vinylidenebis(N,N-dimethylaniline), 4,4'-vinylidenebis(N,N-diethylaniline), 1,1-bis(4-morpholinophenyl)ethylene, 1-phenyl-1-(4-N,N-dimethylaminophenyl)ethylene, etc.
  • the epoxy compound which is a modifying agent having a nitrogen atom-containing group, is not limited to the following, but examples thereof include a hydrocarbon compound containing an epoxy group bonded to an amino group, and may further have an epoxy group bonded to an ether group.
  • Such an epoxy compound is not limited to the following, but may be, for example, an epoxy compound represented by the general formula (a).
  • R is a divalent or higher organic group having at least one polar group selected from a divalent or higher hydrocarbon group, or an oxygen-containing polar group such as an ether, epoxy, or ketone, a sulfur-containing polar group such as a thioether or thioketone, or a nitrogen-containing polar group such as a tertiary amino group or an imino group.
  • the divalent or higher hydrocarbon group may be a saturated or unsaturated straight-chain, branched or cyclic hydrocarbon group, and includes alkylene groups, alkenylene groups, phenylene groups, etc. Preferably, it is a hydrocarbon group having 1 to 20 carbon atoms. Examples include methylene, ethylene, butylene, cyclohexylene, 1,3-bis(methylene)-cyclohexane, 1,3-bis(ethylene)-cyclohexane, o-, m-, p-phenylene, m-, p-xylene, bis(phenylene)-methane, etc.
  • R 1 and R 4 are hydrocarbon groups having 1 to 10 carbon atoms, and R 1 and R 4 may be the same or different.
  • R 2 and R 5 are hydrogen or a hydrocarbon group having 1 to 10 carbon atoms, and R 2 and R 5 may be the same or different.
  • R 3 is a hydrocarbon group having 1 to 10 carbon atoms or a structure represented by the following formula (a1).
  • R 1 , R 2 and R 3 may be bonded to each other to form a cyclic structure.
  • R3 when R3 is a hydrocarbon group, it may be a cyclic structure bonded to R. In the case of the cyclic structure, the N bonded to R3 and R may be directly bonded to each other.
  • n is an integer of 1 or more
  • m is 0 or an integer of 1 or more.
  • R 1 and R 2 are defined in the same manner as R 1 and R 2 in the formula (a), and R 1 and R 2 may be the same or different.
  • the compound As an epoxy compound that is a modifier having a nitrogen atom-containing group, it is preferable that the compound has an epoxy group-containing hydrocarbon group, and more preferably, that the compound has a glycidyl group-containing hydrocarbon group.
  • the epoxy group-containing hydrocarbon group bonded to the amino group or ether group is not particularly limited, but examples thereof include a glycidylamino group, a diglycidylamino group, and a glycidoxy group. More preferred epoxy compounds that are the modifiers are epoxy group-containing compounds that have a glycidylamino group or a diglycidylamino group, and a glycidoxy group, respectively, and examples thereof include compounds represented by the following general formula (a2).
  • R is defined as the same as R in the formula (a), and R6 is a hydrocarbon group having 1 to 10 carbon atoms or a structure represented by the following formula (a3).
  • R6 is a hydrocarbon group, it may be bonded to R to form a cyclic structure, and in this case, the N bonded to R6 and R may be directly bonded to each other.
  • n is an integer of 1 or more
  • m is 0 or an integer of 1 or more.
  • the epoxy compound which is a modifier having a nitrogen atom-containing group, is particularly preferably a compound having one or more diglycidylamino groups and one or more glycidoxy groups in the molecule.
  • Epoxy compounds used as modifiers having a nitrogen atom-containing group include, but are not limited to, N,N-diglycidyl-4-glycidoxyaniline, 1-N,N-diglycidylaminomethyl-4-glycidoxy-cyclohexane, 4-(4-glycidoxyphenyl)-(N,N-diglycidyl)aniline, 4-(4-glycidoxyphenoxy)-(N,N-diglycidyl)aniline, 4-(4-glycidoxybenzyl)-(N,N-diglycidyl)aniline, 4-(N,N'-diglycidyl-2-piperazinyl)-glycidoxybenzene, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, N,N,N',N'-tetraglycidyl-m -xylenediamine, 4,4-methylene-bis(N,N-diglycidylaniline), 1,4-
  • the modifying agent is preferably an alkoxysilane compound having a nitrogen atom-containing group.
  • Such modifying agents are not limited to the following, but include, for example, 3-dimethylaminopropyltrimethoxysilane, 3-dimethylaminopropylmethyldimethoxysilane, 3-diethylaminopropyltriethoxysilane, 3-morpholinopropyltrimethoxysilane, 3-piperidinopropyltriethoxysilane, 3-hexamethyleneiminopropylmethyldiethoxysilane, 3-(4-methyl-1-piperazino)propyltriethoxysilane, 1-[3-(triethoxysilyl)-propyl]-3-methylhexahydropyrimidine, 3-(4-trimethylsilyl ...
  • alkoxysilane compound having a nitrogen atom-containing group include the following: Specifically, tris(3-trimethoxysilylpropyl)amine, tris(3-triethoxysilylpropyl)amine, tris(3-tripropoxysilylpropyl)amine, bis(3-trimethoxysilylpropyl)-[3-(2,2-dimethoxy-1-aza-2-silacyclopentane)propyl]amine, tetrakis(3-trimethoxysilylpropyl)-1,3-propanediamine (also referred to as "N,N,N',N'-tetrakis(3-trimethoxysilylpropyl)-1,3-propanediamine").
  • examples of protected amine compounds in which active hydrogen is substituted with a protecting group include compounds having alkoxysilanes and protected amines in the molecule.
  • examples of such compounds include, but are not limited to, N,N-bis(trimethylsilyl)aminopropyl trimethoxysilane, N,N-bis(trimethylsilyl)aminopropyl methyl dimethoxysilane, N,N-bis(trimethylsilyl)aminopropyl triethoxysilane, N,N-bis(trimethylsilyl)aminopropyl methyl diethoxysilane, N,N-bis(trimethylsilyl)aminoethyl trimethoxysilane, N,N-bis(trimethylsilyl)aminoethyl methyl diethoxysilane, N,N-bis(triethylsilyl)aminopropyl methyl diethoxysilane, N,N-bis(triethy
  • N-(1,3-dimethylbutylidene)-3-methyl(dimethoxysilyl)-1-propanamine N-(1,3-dimethylbutylidene)-3-methyl(diethoxysilyl)-1-propanamine
  • N-(1-methylethylidene)-3-(triethoxysilyl)-1-propanamine N-(1-methylethylidene)-3-(triethoxysilyl)-1-propanamine
  • N-(1-methylethylidene)-3-methyl(dimethoxysilyl)-1-propanamine N-(1-methylethylidene)-3-methyl(diethoxysilyl)-1-propanamine
  • N-ethylidene-3-(triethoxysilyl)-1-propanamine N-ethylidene-3-(trimethoxysilyl)-1-propanamine
  • a modifier having a nitrogen atom-containing group represented by any one of the following formulas (A) to (D) in the coupling step may be used alone or in combination of two or more.
  • R 10 and R 11 are hydrocarbon groups having 1 to 12 carbon atoms, which may contain unsaturated bonds, and may be the same or different
  • R 12 is a hydrocarbon group having 1 to 20 carbon atoms
  • R 8 and R 9 are aliphatic hydrocarbon groups having 1 to 6 carbon atoms, which may contain an unsaturated bond, and may be the same or different
  • R 7 is a hydrocarbon group having 1 to 20 carbon atoms which contains Si, O, or N and may be substituted with an organic group having no active hydrogen, and may contain an unsaturated bond.
  • a is an integer from 1 to 3.
  • A represents a hydrocarbon group having 1 to 20 carbon atoms, or an organic group having at least one atom selected from the group consisting of an oxygen atom, a nitrogen atom, a silicon atom, a sulfur atom, and a phosphorus atom and having no active hydrogen.
  • R 13 , R 14 , and R 15 each independently represent a single bond or an alkylene group having 1 to 20 carbon atoms.
  • R 16 , R 17 , R 18 , R 19 , and R 21 each independently represent an alkyl group having 1 to 20 carbon atoms.
  • R 20 and R 22 each independently represent an alkylene group having 1 to 20 carbon atoms.
  • Each R 23 independently represents an alkyl group having 1 to 20 carbon atoms or a trialkylsilyl group.
  • Each b is independently an integer of 1 to 3
  • each c is independently 1 or 2
  • each i is an integer of 0 to 6
  • each j is an integer of 0 to 6
  • each k is an integer of 0 to 6, and the sum of i, j, and k is an integer of 4 to 10.
  • R 24 , R 25 , R 26 , R 27 , R 28 , and R 29 each independently represent an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms.
  • R 30 , R 31 , and R 32 each independently represent an alkylene group having 1 to 20 carbon atoms.
  • s, t, and u each independently represent an integer of 1 to 3, and the sum of s, t, and u is an integer of 4 or greater.
  • B 1 and B 2 are each independently a divalent hydrocarbon group having 1 to 20 carbon atoms which may or may not contain an oxygen atom.
  • R 33 to R 36 are each independently a monovalent hydrocarbon group having 1 to 20 carbon atoms.
  • L 1 to L 4 are each independently a divalent, trivalent, or tetravalent alkylsilyl group substituted with an alkyl group having 1 to 10 carbon atoms, or a monovalent hydrocarbon group having 1 to 20 carbon atoms; or L 1 and L 2 , and L 3 and L 4 may be linked together to form a ring having 1 to 5 carbon atoms, and when L 1 and L 2 , and L 3 and L 4 are linked together to form a ring, the formed ring may contain 1 to 3 heteroatoms of one or more types selected from the group consisting of N, O, and S.
  • B1 and B2 are each independently an alkylene group having 1 to 10 carbon atoms
  • R33 to R36 are each independently an alkyl group having 1 to 10 carbon atoms
  • L1 to L4 are each independently a tetravalent alkylsilyl group substituted with an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 10 carbon atoms; or L1 and L2 , and L3 and L4 may be linked to each other to form a ring having 1 to 3 carbon atoms, and when L1 and L2 , and L3 and L4 are linked to each other to form a ring, the formed ring may contain 1 to 3 heteroatoms selected from the group consisting of N, O, and S.
  • Examples of the coupling modifier represented by formula (A) include, but are not limited to, 1-methyl-4-[3-(trimethoxysilyl)propyl]piperazine, 1-methyl-4-[3-(triethoxysilyl)propyl]piperazine, 1-propyl-4-[3-(trimethoxysilyl)propyl]piperazine, 1-propyl-4-[3-(triethoxysilyl)propyl]piperazine, 1-trimethylsilyl-4-[3-(trimethoxysilyl)propyl]piperazine, and 1-trimethylsilyl-4-[3-(triethoxysilyl)propyl]piperazine.
  • a in formula (A) is 3.
  • the reaction temperature and reaction time are not particularly limited, but the reaction is preferably carried out at a temperature of 0°C or higher and 120°C or lower, and preferably for 30 seconds or longer.
  • the amount of the coupling modifier represented by formula (A) added is preferably in a range in which the total number of moles of alkoxy groups bonded to silyl groups in the compound represented by formula (A) is 0.2 to 2.0 times the number of moles of the polymerization initiator added, more preferably in a range in which the total number of moles is 0.3 to 1.5 times, and even more preferably in a range in which the total number of moles is 0.4 to 1.0 times. From the viewpoint of setting the molecular weight of the resulting modified conjugated diene polymer in a more preferable range, it is preferably 0.2 times or more, and from the viewpoint of storage stability during long-term storage, it is preferably 2.0 times or less.
  • the amount of the polymerization initiator and the coupling modifier represented by formula (A) added may be adjusted so that the number of moles of the coupling modifier represented by formula (A) is preferably 0.1 to 1.0 times the number of moles of the polymerization initiator.
  • A is preferably represented by any one of the following formulas (I) to (IV).
  • D 1 represents a single bond or a divalent hydrocarbon group having 1 to 20 carbon atoms, and h represents an integer of 1 to 10. When a plurality of D 1 are present, each D 1 is independent.
  • D2 represents a single bond or a divalent hydrocarbon group having 1 to 20 carbon atoms.
  • D3 represents an alkyl group having 1 to 20 carbon atoms.
  • h represents an integer of 1 to 10.
  • D4 represents a single bond or a divalent hydrocarbon group having 1 to 20 carbon atoms.
  • h represents an integer of 1 to 10.
  • D5 represents a single bond or a divalent hydrocarbon group having 1 to 20 carbon atoms, and h represents an integer of 1 to 10. When a plurality of D5s are present, they are each independent of each other.
  • examples of the coupling modifier include, but are not limited to, tris(3-trimethoxysilylpropyl)amine, bis(3-trimethoxysilylpropyl)-[3-(2,2-dimethoxy-1-aza-2-silacyclopentane)propyl]amine, bis[3-(2,2-dimethoxy-1-aza-2-silacyclopentane)propyl]-(3-trimethoxysilylpropyl)amine, tris[3-(2,2-dimethoxy-1-aza-2-silacyclopentane)propyl]amine, tris(3-ethoxysilylpropyl)amine, bis(3-triethoxysilylpropyl)-[3-(2,2-diethoxy-1-aza-2-silacyclopentane)propyl]amine, bis[3-(2,2-diethoxy-1 -aza-2-silacyclopentane)propyl]amine, bis[3-(
  • tetrakis[3-(2,2-dimethoxy-1-aza-2-silacyclopentane)propyl]-1,3-propanediamine tris(3-trimethoxysilylpropyl)-[3-(1-methoxy-2-trimethylsilyl-1-sila-2-azacyclopentane)propyl]-1,3-propanediamine, bis(3-trimethoxysilylpropyl)-[3-(2,2-dimethoxy-1-aza-2-silacyclopentane)propyl]-[3-(1-methoxy-2-trimethylsilyl-1-sila-2-azacyclopentane)propyl]-1,3-propanediamine, bis[3-(2,2-dimethoxy-1-aza-2-silacyclopentane)propyl] propyl]-(3-trimethoxysilylpropyl)-[3-(1-methoxy-2
  • examples of the coupling modifier include, but are not limited to, tris(3-trimethoxysilylpropyl)-methyl-1,3-propanediamine, bis(2-trimethoxysilylpropyl)-[3-(2,2-dimethoxy-1-aza-2-silacyclopentane)propyl]-methyl-1,3-propanediamine, bis[3-(2,2-dimethoxy-1-aza-2-silacyclopentane)propyl]-(3-trimethoxysilylpropyl)-methyl-1,3-propanediamine, bis(2-triethoxysilylpropyl)-methyl-1,3-propanediamine, tris(3-triethoxysilylpropyl)-methyl-1,3-propanediamine, bis(2-triethoxysilylpropyl)-[3-(2,2-diethoxy-1-aza-2-silacyclopentane
  • examples of the coupling modifier include, but are not limited to, tetrakis[3-(2,2-dimethoxy-1-aza-2-silacyclopentane)propyl]silane, tris[3-(2,2-dimethoxy-1-aza-2-silacyclopentane)propyl]-(3-trimethoxysilylpropyl)silane, tris[3-(2,2-dimethoxy-1-aza-2-silacyclopentane)propyl]-(3-trimethoxysilylpropyl)silane, silane, bis(3-trimethoxysilylpropyl)-bis[3-(2,2-dimethoxy-1-aza-2-silacyclopentane)propyl]silane, (3-trimethoxysilyl)-[3-(1-methoxy-2-trimethylsilyl-1-sila-2-azacyclopent
  • examples of the coupling modifier include, but are not limited to, 3-tris[2-(2,2-dimethoxy-1-aza-2-silacyclopentane)ethoxy]silyl-1-(2,2-dimethoxy-1-aza-2-silacyclopentane)propane and 3-tris[2-(2,2-dimethoxy-1-aza-2-silacyclopentane)ethoxy]silyl-1-trimethoxysilylpropane.
  • the amount of the modifier represented by formula (B) added is preferably determined based on the ratio of the number of moles of the polymerization initiator added to the number of moles of the modifier represented by formula (B) added. In this way, the conjugated diene polymer and the modifier can be adjusted to react in a desired stoichiometric ratio.
  • the amount of the polymerization initiator and the coupling modifier represented by formula (B) added may be adjusted so that the number of moles of the coupling modifier represented by formula (B) is preferably 0.012 to 1.0 times, more preferably 0.02 to 0.5 times, relative to the number of moles of the polymerization initiator.
  • the number of functional groups of the modifier (for example, when i and j are 2 or more and w and x are present in a plurality of cases, and when f and g are equal, it is f ⁇ i+(g+1) ⁇ j+k) is preferably an integer of 5 to 10, more preferably an integer of 6 to 10. From the viewpoint of setting the molecular weight of the resulting modified conjugated diene polymer in a preferred range, it is preferably 0.012 times or more. Also, from the viewpoint of storage stability during long-term storage, it is preferably 0.2 times or less.
  • i, j, and k in the formula (B) are all 3.
  • Coupling modifiers represented by formula (C) include, but are not limited to, tris(3-trimethoxysilylpropyl)amine, tris(3-methyldimethoxysilylpropyl)amine, tris(3-triethoxysilylpropyl)amine, tris(3-methyldiethoxysilylpropyl)amine, tris(trimethoxysilylmethyl)amine, tris(2-trimethoxysilylethyl)amine, and tris(4-trimethoxysilylbutyl)amine.
  • reaction temperature and reaction time are not limited to the following, but are preferably from 0°C to 120°C, and the reaction is preferably carried out for 30 seconds or more.
  • the amount of the coupling modifier represented by formula (C) added is preferably in a range such that the total number of moles of alkoxy groups bonded to silyl groups in the compound represented by formula (C) is 0.1 to 2.0 times the number of moles of the polymerization initiator added, more preferably 0.2 to 1.0 times, and even more preferably 0.3 to 0.5 times. From the viewpoint of the molecular weight of the resulting modified conjugated diene polymer, it is preferable to set the amount to 0.1 times or more. Also, from the viewpoint of storage stability during long-term storage, it is preferable to set the amount to 2.0 times or less.
  • Examples of the coupling modifier represented by formula (D) include 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-dimethyl propane-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,
  • the reaction temperature and reaction time are not particularly limited, but the reaction is preferably carried out at a temperature of 0°C or higher and 120°C or lower, and preferably for 30 seconds or longer.
  • the amount of the coupling modifier represented by formula (D) added is preferably in a range in which the total number of moles of alkoxy groups bonded to silyl groups in the compound represented by formula (D) is 0.25 to 2.0 times the number of moles of the polymerization initiator added, more preferably in a range in which the total number of moles is 0.3 to 1, and even more preferably in a range in which the total number of moles is 0.35 to 0.5. From the viewpoint of the molecular weight of the resulting modified conjugated diene polymer and from the viewpoint of storage stability during long-term storage, it is preferably 2.0 times or less.
  • the method for producing a conjugated diene polymer of this embodiment may include a condensation reaction step in which a condensation promoter is added after and/or before the coupling step to cause a condensation reaction.
  • a deactivator and/or a neutralizer may be added to the polymer solution, if necessary.
  • quenching agents include, but are not limited to, water and alcohols such as methanol, ethanol, and isopropanol.
  • the neutralizing agent include, but are not limited to, carboxylic acids such as stearic acid, oleic acid, and versatic acid (a mixture of highly branched carboxylic acids having 9 to 11 carbon atoms and mainly having 10 carbon atoms), aqueous solutions of inorganic acids, and carbon dioxide gas.
  • a rubber stabilizer is preferably added from the viewpoint of preventing gel formation after polymerization and improving stability during processing.
  • the rubber stabilizer is not limited to the following and any known stabilizer can be used.
  • antioxidants such as 2,6-di-tert-butyl-4-hydroxytoluene (BHT), n-octadecyl-3-(4'-hydroxy-3',5'-di-tert-butylphenol)propionate, and 2-methyl-4,6-bis[(octylthio)methyl]phenol are preferred.
  • the method for producing a conjugated diene polymer of the present embodiment may include a step of obtaining the obtained conjugated diene polymer from the polymer solution.
  • a method for obtaining a conjugated diene polymer from a polymer solution a known method may be used, and for example, the following method may be used.
  • Examples of the method include a method in which the solvent is separated by steam stripping or the like, the conjugated diene polymer is filtered, and then dehydrated and dried to obtain a conjugated diene polymer, a method in which the conjugated diene polymer is concentrated in a flashing tank and further devolatilized by a vent extruder or the like to obtain a conjugated diene polymer, and a method in which the conjugated diene polymer is directly devolatilized by a drum dryer or the like to obtain a conjugated diene polymer.
  • Step of Obtaining Extended Conjugated Diene Polymer In the method for producing a conjugated diene polymer of the present embodiment, at least one selected from the group consisting of an extending oil, a liquid rubber, and a resin may be further added to the produced conjugated diene polymer to obtain an extended conjugated diene polymer.
  • the extended conjugated diene polymer includes not only oil-extended conjugated diene polymers containing oil, but also those containing liquid polybutadiene and various resins other than oil. This can further improve the processability of the conjugated diene polymer.
  • the method for adding the extender oil to the conjugated diene polymer is not limited to the following method, but a method in which the extender oil is added to a conjugated diene polymer solution, mixed, and the extended polymer solution is desolvated is preferred.
  • the extender oil include aromatic oil, naphthenic oil, paraffin oil, vegetable oil, etc.
  • the vegetable oil can be made from an oil selected from the group consisting of linseed oil, safflower oil, soybean oil, corn oil, cottonseed oil, castor oil, tung oil, pine oil, sunflower oil, palm oil, olive oil, coconut oil, peanut oil and grape seed oil.
  • aromatic substitute oils having a polycyclic aromatic (PCA) component of 3 mass% or less according to the IP346 method are preferred.
  • PCA polycyclic aromatic
  • Examples of aromatic substitute oils include Treated Distillate Aromatic Extracts (TDAE) and Mild Extraction Solvate (MES) as shown in Kautschuk Kunststoffe 52(12)799 (1999), as well as Residual Aromatic Extracts (RAE).
  • liquid rubber examples include, but are not limited to, liquid polybutadiene, liquid styrene-butadiene rubber, and the like.
  • resins include, but are not limited to, aromatic petroleum resins, coumarone-indene resins, terpene resins, rosin derivatives (including paulownia oil resins), tall oil, derivatives of tall oil, rosin ester resins, natural and synthetic terpene resins, aliphatic hydrocarbon resins, aromatic hydrocarbon resins, mixed aliphatic-aromatic hydrocarbon resins, coumarin-indene resins, phenolic resins, p-tert-butylphenol-acetylene resins, phenol-formaldehyde resins, xylene-formaldehyde resins, monoolefin oligomers, diolefin oligomers, hydrogenated aromatic hydrocarbon resins, cyclic aliphatic hydrocarbon resins, hydrogenated hydrocarbon resins, hydrogenated paul
  • the amount of at least one selected from the group consisting of extender oil, liquid rubber, and resin is not particularly limited, but is preferably 1 to 60 parts by mass, more preferably 10 to 60 parts by mass, and even more preferably 15 to 37.5 parts by mass, relative to 100 parts by mass of the conjugated diene-based polymer of the present embodiment.
  • the conjugated diene-based polymer of the present embodiment can be made into a rubber composition by adding a filler (hereinafter, may be referred to as the rubber composition of the present embodiment).
  • the rubber composition of the present embodiment includes a rubber component containing the conjugated diene polymer of the present embodiment described above, and a filler of 5.0 parts by mass or more and 150 parts by mass or less per 100 parts by mass of the rubber component, and the rubber component preferably contains 10 parts by mass or more of the conjugated diene polymer of the present embodiment per 100 parts by mass of the total amount of the rubber component.
  • a rubber composition By dispersing the filler in the rubber component containing the conjugated diene polymer of the present embodiment, a rubber composition can be obtained that is more excellent in processability during vulcanization, and the vulcanizate has more excellent low hysteresis loss properties, fracture properties, and abrasion resistance.
  • the rubber component containing the conjugated diene polymer of the present embodiment at a predetermined ratio the low hysteresis loss performance, processability, and abrasion resistance tend to be further improved.
  • Fillers include, but are not limited to, silica-based inorganic fillers, carbon black, metal oxides, and metal hydroxides. Among these, silica-based inorganic fillers are preferred. In particular, when the rubber composition of this embodiment is used for vulcanized rubber applications such as tires, automobile parts such as anti-vibration rubber, and shoes, it is preferred that the rubber composition contains a silica-based inorganic filler. Such fillers may be used alone or in combination of two or more types.
  • the silica-based inorganic filler is not particularly limited and any known filler can be used, but solid particles containing SiO2 or Si3Al as a structural unit are preferred, and solid particles containing SiO2 or Si3Al as a main component of the structural unit are more preferred.
  • the main component refers to a component contained in the silica-based inorganic filler in an amount of more than 50 mass%, preferably 70 mass% or more, more preferably 80 mass% or more.
  • Silica-based inorganic fillers include, but are not limited to, inorganic fibrous substances such as silica, clay, talc, mica, diatomaceous earth, wollastonite, montmorillonite, zeolite, and glass fiber. Silica-based inorganic fillers with hydrophobic surfaces and mixtures of silica-based inorganic fillers and non-silica-based inorganic fillers may also be used. Among these, silica or glass fiber is preferred, and silica is more preferred, from the viewpoint of further improving the strength and abrasion resistance of the rubber composition of this embodiment. Silica is not particularly limited, but examples include dry silica, wet silica, and synthetic silicate silica. Among these silicas, wet silica is preferred, from the viewpoint of further improving the breaking strength of the rubber composition.
  • the nitrogen adsorption specific surface area of the silica-based inorganic filler determined by the BET adsorption method is preferably 100 m 2 /g or more and 300 m 2 /g or less, more preferably 170 m 2 /g or more and 250 m 2 /g or less. If necessary, a silica-based inorganic filler having a relatively small specific surface area (for example, a specific surface area of less than 200 m 2 /g) and a silica-based inorganic filler having a relatively large specific surface area (for example, 200 m 2 /g or more) may be used in combination.
  • the rubber composition of this embodiment further improves the dispersibility of silica. As a result, it tends to have better abrasion resistance, fracture strength and low hysteresis loss.
  • carbon black examples include, but are not limited to, carbon black of various classes such as SRF, FEF, HAF, ISAF, and SAF. Among these, carbon black having a nitrogen adsorption specific surface area of 50 m 2 /g or more as determined by the BET adsorption method and a dibutyl phthalate (DBP) oil absorption of 80 mL/100 g or less is preferred.
  • SRF sulfur adsorption specific surface area
  • DBP dibutyl phthalate
  • the metal oxide is not particularly limited as long as it is a solid particle having a structural unit of the chemical formula M x O y (M represents a metal atom, and x and y each independently represent an integer of 1 to 6), and examples thereof include alumina, titanium oxide, magnesium oxide, and zinc oxide.
  • Metal hydroxides include, but are not limited to, aluminum hydroxide, magnesium hydroxide, and zirconium hydroxide.
  • the content of the filler in the rubber composition of this embodiment is preferably 5.0 parts by mass or more and 150 parts by mass or less, more preferably 20 parts by mass or more and 100 parts by mass or less, and even more preferably 30 parts by mass or more and 90 parts by mass or less, per 100 parts by mass of the rubber component.
  • the filler satisfies the above range, the rubber composition tends to have better processability during vulcanization, and the vulcanizate tends to have better low hysteresis loss, fracture properties, and abrasion resistance.
  • the rubber composition of this embodiment preferably contains 0.5 parts by mass or more and 100 parts by mass or less of carbon black per 100 parts by mass of the rubber component containing the conjugated diene polymer of this embodiment.
  • the rubber composition preferably contains 3.0 parts by mass or more and 100 parts by mass or less of carbon black, more preferably 5.0 parts by mass or more and 50 parts by mass or less, per 100 parts by mass of the rubber component containing the conjugated diene polymer of this embodiment.
  • the rubber composition of the present embodiment may further contain a silane coupling agent.
  • a silane coupling agent is preferably, but not limited to, a compound having a sulfur bond and an alkoxysilyl group or a silanol group in one molecule, such as, but not limited to, bis-[3-(triethoxysilyl)-propyl]-tetrasulfide, bis-[3-(triethoxysilyl)-propyl]-disulfide, and bis-[2-(triethoxysilyl)-ethyl]-tetrasulfide.
  • the content of the silane coupling agent is preferably 0.1 parts by mass or more and 30 parts by mass or less, more preferably 0.5 parts by mass or more and 20 parts by mass or less, and even more preferably 1.0 parts by mass or more and 15 parts by mass or less, relative to 100 parts by mass of the filler.
  • the content of the silane coupling agent is within the above range, there is a tendency for the interaction between the rubber component and the filler to be further improved.
  • the rubber composition of the present embodiment may contain, as a rubber component, a rubber-like polymer other than the conjugated diene-based polymer of the present embodiment (hereinafter simply referred to as a "rubber-like polymer").
  • rubber-like polymers include, but are not limited to, conjugated diene polymers and hydrogenated products thereof, random copolymers of conjugated diene compounds and vinyl aromatic compounds and hydrogenated products thereof, block copolymers of conjugated diene compounds and vinyl aromatic compounds and hydrogenated products thereof, non-diene polymers, and natural rubber.
  • rubber-like polymers include, but are not limited to, styrene-based elastomers such as butadiene rubber and hydrogenated products thereof, isoprene rubber and hydrogenated products thereof, styrene-butadiene rubber and hydrogenated products thereof, styrene-butadiene block copolymers and hydrogenated products thereof, and styrene-isoprene block copolymers and hydrogenated products thereof, as well as acrylonitrile-butadiene rubber and hydrogenated products thereof.
  • styrene-based elastomers such as butadiene rubber and hydrogenated products thereof, isoprene rubber and hydrogenated products thereof, styrene-butadiene rubber and hydrogenated products thereof, styrene-butadiene block copolymers and hydrogenated products thereof, and styrene-isoprene block copolymers and hydrogenated products thereof, as well as acrylonitrile-butadiene rubber and
  • non-diene polymers include, but are not limited to, olefin elastomers such as ethylene-propylene rubber, ethylene-propylene-diene rubber, ethylene-butene-diene rubber, ethylene-butene rubber, ethylene-hexene rubber, and ethylene-octene rubber, butyl rubber, brominated butyl rubber, acrylic rubber, fluororubber, silicone rubber, chlorinated polyethylene rubber, epichlorohydrin rubber, ⁇ , ⁇ -unsaturated nitrile-acrylate-conjugated diene copolymer rubber, urethane rubber, and polysulfide rubber.
  • natural rubber include, but are not limited to, smoked sheet RSS 3 to 5, SMR, and epoxidized natural rubber.
  • the rubber-like polymer may be a modified rubber to which a polar functional group such as a hydroxyl group or an amino group has been added.
  • the rubber-like polymer is preferably one or more selected from the group consisting of butadiene rubber, isoprene rubber, styrene-butadiene rubber, natural rubber, and butyl rubber.
  • the weight average molecular weight of the rubber-like polymer is preferably 2,000 to 2,000,000, and more preferably 5,000 to 1,500,000, from the viewpoint of the balance between the abrasion resistance, breaking strength, and low hysteresis loss of the rubber composition and the processability.
  • a low molecular weight rubber-like polymer so-called liquid rubber, can also be used as the rubber-like polymer.
  • These rubber-like polymers may be used alone or in combination of two or more types.
  • the content ratio (mass ratio) of the conjugated diene polymer to the rubber-like polymer is preferably 10/90 or more and 100/0 or less, more preferably 20/80 or more and 99/1 or less, and even more preferably 30/70 or more and 95/5 or less.
  • the rubber component contains the conjugated diene polymer of this embodiment in an amount of preferably 10 parts by mass or more and 100 parts by mass or less, more preferably 20 parts by mass or more and 90 parts by mass or less, and even more preferably 30 parts by mass or more and 80 parts by mass or less, per 100 parts by mass of the total amount of the rubber component.
  • the ratio of the conjugated diene polymer of this embodiment contained in the rubber component is within the above range, the vulcanizate of the rubber composition tends to be even more excellent in wear resistance and low hysteresis loss.
  • a rubber softener may be added in addition to the rubber component.
  • the rubber softener the same ones as those exemplified as those contained in the above-mentioned conjugated diene polymer can be used, but mineral oil or liquid or low molecular weight synthetic softeners are preferred.
  • the rubber composition of the present embodiment preferably contains a rubber softener having a moderate aromatic content. By containing such a rubber softener, compatibility with the conjugated diene polymer is further improved.
  • the content of the rubber softener in the rubber composition of this embodiment is represented by the total amount of the rubber softener added in advance to the conjugated diene polymer or rubber-like polymer and the rubber softener added when preparing the rubber composition.
  • the content of the rubber softener is preferably 0 parts by mass or more and 100 parts by mass or less, more preferably 10 parts by mass or more and 90 parts by mass or less, and even more preferably 30 parts by mass or more and 90 parts by mass or less, per 100 parts by mass of the rubber component.
  • the rubber composition can be produced by mixing a conjugated diene polymer, a rubber-like polymer, a filler, a silane coupling agent, a rubber softener, and the like.
  • a general mixer such as an open roll, a Banbury mixer, a kneader, a single-screw extruder, a twin-screw extruder, or a multi-screw extruder, and a method in which the components are dissolved and mixed and then the solvent is removed by heating.
  • melt-kneading method using a roll, a Banbury mixer, a kneader, or an extruder is preferred from the standpoint of productivity and good kneading properties.
  • the rubber component, the filler, the silane coupling agent, and the additives may be kneaded all at once, or may be mixed in several batches.
  • the rubber composition of this embodiment may be vulcanized with a vulcanizing agent.
  • the vulcanizing agent is not particularly limited, but examples include radical generators such as organic peroxides and azo compounds, oxime compounds, nitroso compounds, polyamine compounds, sulfur, and sulfur compounds.
  • Sulfur compounds include sulfur monochloride, sulfur dichloride, disulfide compounds, and polymeric polysulfur compounds.
  • the content of the vulcanizing agent is preferably 0.01 parts by mass or more and 20 parts by mass or less, and more preferably 0.1 parts by mass or more and 15 parts by mass or less, per 100 parts by mass of the rubber component.
  • the vulcanization method a conventionally known method can be used.
  • the vulcanization temperature is preferably 120°C or more and 200°C or less, and more preferably 140°C or more and 180°C or less.
  • a vulcanization accelerator and/or a vulcanization aid may be used as necessary.
  • the vulcanization accelerator a conventionally known material may be used, and examples thereof include, but are not limited to, sulfenamide-based, guanidine-based, thiuram-based, aldehyde-amine-based, aldehyde-ammonia-based, thiazole-based, thiourea-based, and dithiocarbamate-based vulcanization accelerators.
  • examples of the vulcanization aid include, but are not limited to, zinc oxide and stearic acid.
  • the amount of each of the vulcanization accelerator and the vulcanization aid is preferably 0.01 parts by mass or more and 20 parts by mass or less, and more preferably 0.1 parts by mass or more and 15 parts by mass or less, per 100 parts by mass of the rubber component.
  • the rubber composition of the present embodiment may contain various additives such as softeners other than those described above, other fillers, heat stabilizers, antistatic agents, weather stabilizers, antioxidants, colorants, and lubricants, within the range that does not impair the effects of the present embodiment.
  • softener a known softener can be used.
  • Other fillers include, but are not limited to, calcium carbonate, magnesium carbonate, aluminum sulfate, and barium sulfate.
  • Known materials can be used as the heat stabilizer, antistatic agent, weather stabilizer, antioxidant, colorant, and lubricant.
  • the rubber composition of this embodiment is suitable for use as a rubber composition for tires.
  • the rubber composition of this embodiment is not particularly limited, but can be suitable for use in various parts of tires such as fuel-efficient tires, all-season tires, high-performance tires, and studless tires; for example, the tread, carcass, sidewalls, and bead portions.
  • the amount of bound styrene (mass %) relative to 100 mass % of the sample conjugated diene polymer was measured based on the amount of absorption of ultraviolet light at wavelengths (around 254 nm) by the phenyl group of styrene (measuring device: Shimadzu Corporation spectrophotometer "UV-2450").
  • the bound styrene amount was calculated in the same manner as for the bound styrene amount in the segment of the conjugated diene polymer, except that the sample was changed from the conjugated diene polymer to the first polymer segment.
  • the segment ratio ( r1 ) of the first polymer segment and the segment ratio ( r2 ) of the second polymer segment were calculated by the method described below, and the vinyl bond amount Y2 in the second polymer segment was calculated from the following formula (10) using the bound styrene amount Xall in the conjugated diene polymer, the bound styrene amount X1 in the first polymer segment, the bound styrene amount X2 in the second polymer segment, and the vinyl bond amount Yall in the conjugated diene polymer and the vinyl bond amount Y1 in the first polymer segment, all of which were calculated from the measurements.
  • the first polymer segment ratio was calculated using the following formula (11).
  • the ratio of the polymer segment in the first polymerization step (P1) for preparing the first polymer segment was calculated from the solid amount of the conjugated diene-based polymer per hour after the first polymerization step (P1) relative to the total amount of the conjugated diene compound and the aromatic vinyl compound added per hour in polymerizing the conjugated diene-based polymer.
  • the amount of solids in the conjugated diene polymer solution was determined from the amount of non-volatile components in the polymer solution flowing through the outlet of the first polymerization step (P1) per unit time.
  • the total amount of the polymer solution flowing through the outlet of the first polymerization step (P1) was collected for 3 minutes, and a polymerization terminator was immediately added. Then, the polymer solution was transferred to a heat-resistant dish or the like, and dried in an oven at 140° C. for 30 minutes or more, and the mass M1 of the remaining solid matter was measured.
  • the solid amount m1 and the first polymer segment ratio (r 1 ) were calculated by the formula (11).
  • the second polymer segment ratio (r 2 ) was calculated using the following formula (12).
  • the second polymer segment ratio in the second polymerization step (P2) for forming the second polymer segment was calculated from the difference between the solid amount of the conjugated diene-based polymer per hour after the second polymerization step (P2) and the solid amount of the conjugated diene-based polymer per hour after the first polymerization step (P1), relative to the total amount of the conjugated diene compound and the aromatic vinyl compound added per hour in polymerizing the conjugated diene-based polymer.
  • the amount of solids in the conjugated diene polymer solution was determined from the amount of non-volatile components in the polymer solution flowing from the outlet of the second polymerization step (P2) per unit time.
  • the total amount of the polymer solution flowing through the outlet of the second polymerization step (P2) was collected for 3 minutes, and a polymerization terminator was immediately added.
  • the solution was then transferred to a heat-resistant dish or the like, and the mass M2 of the remaining solid matter was measured when it was dried in a 140°C oven for 30 minutes or more.
  • the second polymer segment ratio r2 was calculated from the solid matter amount M1 and the solid matter mass M2 obtained in the first polymerization step (P1) described above using the formula (12).
  • the eluent used was tetrahydrofuran (THF) containing 5 mmol/L triethylamine.
  • THF tetrahydrofuran
  • the columns used were three Tosoh Corporation products under the trade name "TSKgel SuperMultiporeHZ-H” connected together, and a Tosoh Corporation product under the trade name "TSKguardcolumn SuperMP(HZ)-H” was connected in front of them as a guard column.
  • 10 mg of a measurement sample was dissolved in 10 mL of THF to prepare a measurement solution, and 10 ⁇ L of the measurement solution was injected into a GPC measurement device and measured under conditions of an oven temperature of 40° C. and a THF flow rate of 0.35 mL/min.
  • the extrapolated glass transition onset temperature was determined as the temperature at the intersection of a straight line extending from the low-temperature baseline to the high-temperature side and a tangent drawn at the point where the gradient of the curve of the step-like change in the glass transition is maximum.
  • the extrapolated glass transition end temperature was determined as the temperature at the intersection of a straight line extending from the high-temperature baseline to the low-temperature side and a tangent drawn at the point where the gradient of the curve of the step-like change in the glass transition is maximum.
  • the modification ratios of the conjugated diene polymers of the Examples and Comparative Examples were measured by column adsorption GPC as follows.
  • the conjugated diene polymer was used as a sample, and the measurement was carried out by utilizing the characteristic of the modified basic polymer component being adsorbed in a GPC column filled with silica gel.
  • the amount of a sample solution containing a sample and low molecular weight internal standard polystyrene was adsorbed onto the silica-based column by measuring the difference between the chromatogram measured using a polystyrene-based column and the chromatogram measured using a silica-based column, and the modification rate was calculated.
  • ⁇ Preparation of sample solution> 10 mg of a sample and 5 mg of standard polystyrene were dissolved in 20 mL of THF (tetrahydrofuran) to prepare a sample solution.
  • THF tetrahydrofuran
  • ⁇ GPC measurement conditions using polystyrene column> A Tosoh Corporation product name "HLC-8320GPC” was used, and 10 ⁇ L of the sample solution was injected into the device using THF containing 5 mmol/L triethylamine as an eluent.
  • a chromatogram was obtained using an RI detector under the conditions of a column oven temperature of 40° C. and a THF flow rate of 0.35 mL/min.
  • the columns used were three Tosoh Corporation products under the trade name "TSKgel SuperMultiporeHZ-H” connected together, and a Tosoh Corporation product under the trade name “TSKguardcolumn SuperMP(HZ)-H” was connected in front of them as a guard column.
  • THF was used as an eluent
  • 50 ⁇ L of the sample solution was injected into the apparatus, and a chromatogram was obtained under the conditions of a column oven temperature of 40° C.
  • the columns used were Agilent Corporation's Zorbax PSM-1000S, PSM-300S, and PSM-60S, connected in this order, with a DIOL 4.6 ⁇ 12.5 mm 5 micron guard column connected in front of them.
  • Example 1 Two tank-type pressure vessels each having an internal volume of 10 L, an internal height (L) to diameter (D) ratio (L/D) of 4.0, an inlet at the bottom and an outlet at the top, and equipped with an agitator as a tank-type reactor and a jacket for temperature control were connected together as polymerization reactors. 1,3-butadiene, which had been previously dehydrated, was mixed at 18.8 g/min and normal hexane was mixed at 163.4 g/min to obtain a mixed solution.
  • n-butyllithium for inactivating remaining impurities was added at 0.104 mmol/min, mixed, and then continuously supplied to the bottom of the reaction unit. Furthermore, 2,2-bis(2-oxolanyl)propane as a polar substance was supplied at a rate of 0.027 mmol/min, and n-butyllithium as a polymerization initiator was supplied at a rate of 0.239 mmol/min to the bottom of the first reactor, which was vigorously mixed with a stirrer, and the temperature inside the reactor was maintained at 78°C.
  • the polymer solution was continuously fed from the top of the first reactor to the bottom of the second reactor, and further to the second reactor, 1,3-butadiene was added at a rate of 10.6 g/min, styrene at 4.5 g/min, normal hexane at 41.9 g/min, and 2,2-bis(2-oxolanyl)propane as a polar substance at 0.415 mmol/min while stirring, and the reaction was continued at 78°C.
  • Coupled agent A 1-methyl-4-[3-(trimethoxysilyl)propyl]piperazine
  • coupling agent B tetrakis(3-trimethoxysilylpropyl)-1,3-propanediamine
  • the time until the coupling agent was added to the polymer solution flowing out from the outlet of the reactor was 4.8 minutes, the temperature was 68°C, and the difference between the temperature in the polymerization process and the temperature before the coupling agent was added was 2°C.
  • a small amount of the conjugated diene polymer solution after the coupling reaction was withdrawn, and an antioxidant (BHT) was added in an amount of 0.2 g per 100 g of the polymer.
  • BHT antioxidant
  • an antioxidant BHT was continuously added to the polymer solution after the coupling reaction at 0.055 g/min (n-hexane solution) so that the amount was 0.2 g per 100 g of polymer, and the coupling reaction was terminated.
  • SRAE oil JOMO Process NC140, manufactured by JX Nippon Oil & Energy Corporation
  • the solvent was removed by steam stripping to obtain a conjugated diene polymer (A1). The molecular weight, Mooney viscosity, and modification rate of the polymer were determined.
  • Example 2 To the first unit, 1,3-butadiene was added at 15.8 g/min and normal hexane at 156.0 g/min, and 2,2-bis(2-oxolanyl)propane was added as a polar substance at a rate of 0.072 mmol/min, and to the second unit, 1,3-butadiene was added at 14.0 g/min, styrene at 4.4 g/min, normal hexane at 49.9 g/min, and 2,2-bis(2-oxolanyl)propane was added as a polar substance at a rate of 0.370 mmol/min. The other conditions were the same as in Example 1, and a conjugated diene polymer (A2) was obtained.
  • A2 conjugated diene polymer
  • Example 3 To the first reactor, 1,3-butadiene was added at 19.8 g/min and normal hexane at 165.6 g/min, and 2,2-bis(2-oxolanyl)propane was added as a polar substance at a rate of 0.145 mmol/min, and to the second reactor, 1,3-butadiene was added at 7.2 g/min, styrene at 4.2 g/min, normal hexane at 33.2 g/min, and 2,2-bis(2-oxolanyl)propane as a polar substance at a rate of 0.253 mmol/min, and the internal temperature of the second reactor was set to 78° C. Other conditions were the same as in Example 1, and a conjugated diene polymer (A3) was obtained.
  • A3 conjugated diene polymer
  • Example 4 To the first reactor, 1,3-butadiene was added at 18.8 g/min and normal hexane at 163.4 g/min, 2,2-bis(2-oxolanyl)propane was added as a polar substance at a rate of 0.023 mmol/min, and the internal temperature of the first reactor was set to 82° C. Furthermore, to the second reactor, 1,3-butadiene was added at 11.2 g/min, styrene at 5.3 g/min, normal hexane at 44.8 g/min, and 2,2-bis(2-oxolanyl)propane as a polar substance at a rate of 0.153 mmol/min. The other conditions were the same as in Example 1, and a conjugated diene polymer (A4) was obtained.
  • A4 conjugated diene polymer
  • Example 5 As a coupling agent, 1-methyl-4-[3-(trimethoxysilyl)propyl]piperazine (referred to as “coupling agent A” in the table) was continuously added at a rate of 0.110 mmol/min, and tetrakis(3-trimethoxysilylpropyl)-1,3-propanediamine (referred to as “coupling agent B” in the table) was continuously added at a rate of 0.007 mmol/min. The other conditions were the same as in Example 1, and a conjugated diene polymer (A5) was obtained.
  • coupling agent A 1-methyl-4-[3-(trimethoxysilyl)propyl]piperazine
  • coupling agent B tetrakis(3-trimethoxysilylpropyl)-1,3-propanediamine
  • Example 6 The polymerization initiator added to the first reactor was n-butyllithium at 0.193 mmol/min, the polar substance added to the second reactor was 2,2-bis(2-oxolanyl)propane at 0.019 mmol/min, and the coupling agent added to the second reactor was 2,2-bis(2-oxolanyl)propane at 0.298 mmol/min.
  • the other conditions were the same as in Example 1, and a conjugated diene polymer (A6) was obtained.
  • Example 7 The polymerization initiator added to the first reactor was n-butyllithium at 0.343 mmol/min, the polar substance added to the second reactor was 2,2-bis(2-oxolanyl)propane at 0.033 mmol/min, and the coupling agent added to the second reactor was 1-methyl-4-[3-(trimethoxysilyl)propyl]piperazine (referred to as "coupling agent A" in the table) at 0.173 mmol/min.
  • the other conditions were the same as in Example 1, and a conjugated diene polymer (A7) was obtained.
  • Example 8 The polymerization initiator added to the first reactor was n-butyllithium at 0.198 mmol/min, the polar substance added to the second reactor was 2,2-bis(2-oxolanyl)propane at 0.019 mmol/min, and the coupling agent added to the second reactor was 2,2-dimethoxy-1-(3-trimethoxysilylpropyl)-1-aza-2-silacyclopentane (referred to as "coupling agent C" in the table) at 0.052 mmol/min.
  • the other conditions were the same as in Example 1, and a conjugated diene polymer (A8) was obtained.
  • Example 9 The polymerization initiator added to the first reactor was n-butyllithium at 0.130 mmol/min, the polar substance was 2,2-bis(2-oxolanyl)propane at 0.015 mmol/min, the second reactor was 2,2-bis(2-oxolanyl)propane at 0.235 mmol/min, and the coupling agent was tetrakis(3-trimethoxysilylpropyl)-1,3-propanediamine (referred to as "coupling agent B" in the table) at a rate of 0.017 mmol/min.
  • the coupling agent B tetrakis(3-trimethoxysilylpropyl)-1,3-propanediamine
  • SRAE oil (JOMO Process NC140 manufactured by JX Nippon Oil & Energy Corporation) was added continuously to 25.0 g per 100 g of polymer.
  • the other conditions were the same as in Example 1, and a conjugated diene polymer (A9) was obtained.
  • Example 10 1,3-butadiene was continuously added to the second reactor at a rate of 13.8 g/min, styrene was continuously added to the second reactor at a rate of 2.7 g/min, and normal hexane was continuously added to the second reactor at a rate of 46.6 g/min.
  • the other conditions were the same as in Example 4, and a conjugated diene polymer (A10) was obtained.
  • Example 11 As a polar substance to be added to the first reactor, 2,2-bis(2-oxolanyl)propane was continuously added at a rate of 0.266 mmol/min, and to the second reactor, 2,2-bis(2-oxolanyl)propane was continuously added at a rate of 0.176 mmol/min.
  • the other conditions were the same as in Example 1, and a conjugated diene polymer (A11) was obtained.
  • Example 12 To the first reactor, 1,3-butadiene was added at 13.8 g/min and styrene at 4.4 g/min simultaneously, normal hexane was added at 104.8 g/min, 2,2-bis(2-oxolanyl)propane was added as a polar substance at a rate of 0.003 mmol/min, and the internal temperature of the first reactor was set to 65°C.
  • 1,3-butadiene was added at 2.9 g/min, no additional styrene was added, normal hexane was added at 9.5 g/min, and 2,2-bis(2-oxolanyl)propane was added as an additional polar substance at a rate of 0.020 mmol/min, the internal temperature of the second reactor was set to 65° C., and 1-methyl-4-[3-(trimethoxysilyl)propyl]piperazine (referred to as "coupling agent A” in the table) was added as a coupling agent at a rate of 0.087 mmol/min, and tetrakis(3-trimethoxysilylpropyl)-1,3-propanediamine (referred to as "coupling agent B” in the table) was added continuously at 0.009 mmol/min.
  • the other conditions were the same as in Example 1, and a conjugated diene polymer (A12) was obtained.
  • Example 13 The polymerization initiator added to the first reactor was n-butyllithium at 0.370 mmol/min, the polar substance added to the second reactor was 2,2-bis(2-oxolanyl)propane at 0.036 mmol/min, and the other conditions were the same as in Example 7, to obtain a conjugated diene polymer (A13).
  • the polymerization initiator added to the first reactor was n-butyllithium at 0.062 mmol/min, the polar substance was 2,2-bis(2-oxolanyl)propane at 0.007 mmol/min, and the second reactor was 2,2-bis(2-oxolanyl)propane at 0.094 mmol/min.
  • Tetrakis(3-trimethoxysilylpropyl)-1,3-propanediamine referred to as "coupling agent B" in the table
  • SRAE oil (JOMO Process NC140, manufactured by JX Nippon Oil & Energy Corporation) was continuously added as a rubber softener so that the amount was 37.5 g per 100 g of polymer.
  • the other conditions were the same as in Example 9, and a conjugated diene polymer (A14) was obtained.
  • Example 15 To the first reactor, 1,3-butadiene was added at 21.4 g/min, normal hexane at 170.3 g/min, and 2,2-bis(2-oxolanyl)propane was added at 0.054 mmol/min as a polar substance, and to the second reactor, 1,3-butadiene was added at 9.2 g/min, styrene at 3.5 g/min, normal hexane at 36.8 g/min, and 2,2-bis(2-oxolanyl)propane at 0.394 mmol/min. The other conditions were the same as in Example 1, and a conjugated diene polymer (A15) was obtained.
  • Example 16 To the first reactor, 1,3-butadiene was added at 15.4 g/min, normal hexane at 166.0 g/min, and 2,2-bis(2-oxolanyl)propane as a polar substance at 0.072 mmol/min, and to the second reactor, 1,3-butadiene was added at 12.6 g/min, styrene at 5.3 g/min, normal hexane at 48.2 g/min, and 2,2-bis(2-oxolanyl)propane at 0.340 mmol/min, and the polymerization temperature of the second reactor was 80° C. The other conditions were the same as in Example 1, and a conjugated diene polymer (A16) was obtained.
  • A16 conjugated diene polymer
  • a conjugated diene polymer (B2) was obtained in the same manner as in Example 1, except that 2,2-bis(2-oxolanyl)propane was added as a polar substance to the first unit at a rate of 0.266 mmol/min, and 1,3-butadiene was added at 9.7 g/min, additional styrene at 5.4 g/min, normal hexane at 41.3 g/min, and 2,2-bis(2-oxolanyl)propane was added as an additional polar substance to the second unit at a rate of 0.156 mmol/min.
  • a conjugated diene polymer (B4) was obtained in the same manner as in Reference Example 1, except that n-butyllithium was continuously added to the first reactor at a rate of 0.343 mmol/min as a polymerization initiator, 2,2-bis(2-oxolanyl)propane at a rate of 0.124 mmol/min and normal hexane at a rate of 109.2 g/min as a polar substance, and 1-methyl-4-[3-(trimethoxysilyl)propyl]piperazine (referred to as "coupling agent A" in the table) as a coupling agent at a rate of 0.173 mmol/min.
  • coupling agent A 1-methyl-4-[3-(trimethoxysilyl)propyl]piperazine
  • a conjugated diene polymer (B5) was obtained in the same manner as in Reference Example 1, except that n-butyllithium was continuously added to the first reactor at a rate of 0.198 mmol/min as a polymerization initiator, 2,2-bis(2-oxolanyl)propane was continuously added at a rate of 0.070 mmol/min as a polar substance, and 2,2-dimethoxy-1-(3-trimethoxysilylpropyl)-1-aza-2-silacyclopentane (referred to as "coupling agent C" in the table) was continuously added as a coupling agent at a rate of 0.052 mmol/min, and then SRAE oil (JOMO Process NC140, manufactured by JX Nippon Oil & Energy Corporation) was continuously added as a rubber softener in an amount of 25.0 g per 100 g of the polymer.
  • SRAE oil JOMO Process NC140, manufactured by JX Nippon Oil & Energy Corporation
  • a conjugated diene polymer (B6) was obtained in the same manner as in Reference Example 1, except that n-butyllithium was continuously added to the first reactor at a rate of 0.130 mmol/min as a polymerization initiator, 2,2-bis(2-oxolanyl)propane was continuously added to the first reactor at a rate of 0.055 mmol/min as a polar substance, and tetrakis(3-trimethoxysilylpropyl)-1,3-propanediamine (referred to as "coupling agent B" in the table) was continuously added to the first reactor at a rate of 0.017 mmol/min as a coupling agent, and then SRAE oil (JOMO Process NC140, manufactured by JX Nippon Oil & Energy Corporation) was continuously added as a rubber softener in an amount of 37.5 g per 100 g of the polymer.
  • SRAE oil JOMO Process NC140, manufactured by JX Nippon Oil & Energy Corporation
  • Conjugated diene polymers (A1 to A16, B1 to B6): 100 parts by mass (excluding oil) Silica (product name “Ultrasil 7000GR” manufactured by Evonik Degussa, nitrogen adsorption specific surface area 170 m 2 /g): 85.0 parts by mass Carbon black (product name "Seat 7HM (N234)” manufactured by Tokai Carbon Co., Ltd.): 2.0 parts by mass Silane coupling agent (product name "Si69” manufactured by Evonik Degussa, bis(triethoxysilylpropyl)tetrasulfide): 6.8 parts by mass S-RAE oil (product name "Process NC140” manufactured by JX Nippon Oil & Energy Corporation): 40 parts by mass Zinc oxide: 2.4 parts by mass Stearic acid: 1.25 parts by mass Antiaging agent (N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine): 3.5 parts by mass
  • the above materials were kneaded in the following manner to obtain a rubber composition.
  • an internal mixer (capacity 0.3 L) equipped with a temperature control device, the raw rubbers (A1 to A16, B1 to B6), fillers (silica, carbon black), silane coupling agent, process oil, zinc oxide, and stearic acid were kneaded in the first stage of mixing under conditions of a filling rate of 65% and a rotor rotation speed of 30 to 50 rpm.
  • the temperature of the internal mixer was controlled, and each rubber composition (compound) was obtained at a discharge temperature of 145 to 150°C.
  • the mixture obtained above was cooled to room temperature, and then the antioxidant was added and mixed again to improve the dispersion of the silica.
  • the discharge temperature of the mixture was adjusted to 120° C. by controlling the temperature of the mixer.
  • sulfur and vulcanization accelerators 1 and 2 were added and kneaded using an open roll set at 70°C. Thereafter, the product was molded and vulcanized in a vulcanization press at 160° C. for 20 minutes.
  • the rubber composition before vulcanization and the rubber composition after vulcanization were evaluated. Specifically, the evaluation was carried out by the following methods. The evaluation results are shown in Tables 4 to 6.
  • ⁇ Evaluation criteria> 1 50% or less of the edge portion of the sheet is smooth, and the workability is very poor. 2: More than 50% to 60% of the edge portion of the sheet is smooth, and the workability is poor. 3: More than 60% to 80% of the edge portions of the sheet are smooth, and the workability is good. 4: More than 80% to 90% of the edge portions of the sheet are smooth, and the processability is excellent. 5: 90% of the edges of the sheet are super smooth, and the workability is very excellent.
  • the rubber compositions of conjugated diene polymers in Examples 17 to 21, 23, 27 to 29, 31, and 32 which use conjugated diene polymers A1 to A5, A7, A11 to A13, A15, and A16, and which satisfy the difference between the extrapolated glass transition end temperature and the onset temperature being 15°C or more and 35°C or less, were found to have an excellent balance of wet grip performance and low temperature properties when vulcanized, compared to the rubber composition of Reference Example 2, which uses conjugated diene polymer B1.
  • Example 22 which uses conjugated diene polymer A6, was found to have an excellent balance of wet grip performance and low temperature properties when vulcanized, compared to the rubber composition of Comparative Example 7, which uses conjugated diene polymer B3.
  • Example 23 Comparing the rubber compositions of Example 23 to Comparative Example 8, Example 24 to Comparative Example 9, and Example 25 to Comparative Example 10, it was found that the rubber compositions had an excellent balance of wet grip performance and low temperature properties when vulcanized.
  • the rubber compositions of Examples 17 to 24, 26, 27, 29, 31, and 32 which use conjugated diene polymers A1 to A8, A10, A11, A13, A15, and A16, which have a molecular weight distribution of 1.7 or more and 2.5 or less, were found to have excellent processability when vulcanized.
  • the conjugated diene polymer of the present invention has industrial applicability as a material in the fields of tire treads, interior and exterior parts of automobiles, anti-vibration rubber, belts, footwear, foams, various industrial products, and the like.

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