Classifications

• • 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
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B60—VEHICLES IN GENERAL
  • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
  • B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
• • 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
  • C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
  • C08F297/02—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type
  • C08F297/04—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising vinyl aromatic monomers and conjugated dienes
• • 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
  • C08F36/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
  • C08F36/02—Homopolymers and 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
  • C08F36/04—Homopolymers and 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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
  • C08K3/013—Fillers, pigments or reinforcing additives
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L15/00—Compositions of rubber derivatives
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
  • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons

Definitions

• the present invention relates to a modified conjugated diene polymer, a veil, a method for producing a modified conjugated diene polymer, a rubber composition, and a tire.
• Materials that meet the above-mentioned requirements include materials that contain rubber and reinforcing fillers such as carbon black and silica.
• materials that contain rubber and reinforcing fillers such as carbon black and silica.
• a material containing silica it is possible to improve the balance between low hysteresis loss and wet skid resistance.
• attempts have been made to improve the dispersibility of silica in the material by introducing a functional group having affinity or reactivity with silica to the molecular end of a rubber having high mobility, and further to reduce the mobility of the rubber molecular end by bonding with silica particles, thereby reducing hysteresis loss.
• the molecular weight of modified conjugated diene polymers has been increased.
• a high molecular weight modified conjugated diene polymer has a problem in that polymer particles tend to peel off from the surface of a bale of the modified conjugated diene polymer itself, and the area around the molding machine and the area around the conveyor that transports the bale after molding are contaminated with the polymer particles, leaving room for improvement in terms of the working environment.
• the nitrogen atom content in the modified conjugated diene-based polymer increases, which reduces thermal stability and requires the addition of a large amount of antioxidant. From the viewpoints of reducing product costs and reducing environmental load, there is also room for reducing the amount of antioxidant used.
• Patent Document 1 discloses a method of suppressing peeling off of polymer particles from the surface of a veil by adding a process oil to a solution of a conjugated diene polymer to obtain an oil-extended conjugated diene polymer.
• Patent Documents 2 and 3 propose polymers functionalized by reacting a cyclic azasilacycle compound with an active terminal of the polymer.
• Patent Documents 4 and 5 propose diene rubbers obtained by subjecting active terminals of a polymer to a coupling reaction with a polyfunctional silane compound.
• modified conjugated diene polymers have generally been oil-extended modified conjugated diene polymers to which process oil has been added, from the viewpoint of improving bale moldability and processability after kneading.
• process oil has been added to conjugated diene polymers as much as possible.
• the present inventors have found that a modified conjugated diene polymer having a predetermined Mooney viscosity, Mooney relaxation rate (MSR), a glass transition temperature in a predetermined range, and a predetermined silicon atom content and nitrogen atom content can be molded into a bale molded body with a reduced antioxidant content.
• MSR Mooney viscosity
• MMR Mooney relaxation rate
• the present invention is as follows.
• the coupling structure having a nitrogen-containing alkoxysilane substituent at its center is characterized in that the nitrogen-containing alkoxysilane modifier residue has at least four silicon atoms and an alkoxy group and/or a hydroxy group,
• the modified conjugated diene polymer according to any one of [1] to [9], wherein a modified conjugated diene polymer chain having a main chain branched structure is bonded to the silicon atom, and the number of the alkoxy groups and/or the hydroxyl groups in the modifying agent residue is, on average, greater than the number of the silicon atoms.
• a veil comprising 100 parts by mass of the modified conjugated diene polymer according to any one of [1] to [10] and 2 parts by mass or less of a softener component.
• a veil comprising 100 parts by mass of the modified conjugated diene polymer according to any one of [1] to [10] and less than 1 part by mass of a softener component.
• a method for producing the modified conjugated diene polymer according to any one of [1] to [10], A step of polymerizing at least a conjugated diene compound in the presence of an organolithium compound having at least one nitrogen atom in the molecule; a branching step of obtaining a branched conjugated diene polymer having a main chain branched structure by using a branching agent; having The method for producing a modified conjugated diene polymer, wherein in a step of coupling the branched conjugated diene polymer with a coupling agent and/or a step of modifying the branched conjugated diene polymer with a modifying agent having a nitrogen atom-containing group, the coupling agent and/or the modifying agent are added in excess.
• the rubber component contains 10 parts by mass or more of the modified conjugated diene-based polymer according to any one of [1] to [10] or the veil according to [11] or [12], relative to 100 parts by mass of the total amount of the rubber component.
• [15] A tire comprising the rubber composition according to [14].
• the present invention provides a modified conjugated diene polymer that has excellent fuel-saving performance and processability, and has excellent bale moldability even when it is a non-oil-extended product that does not contain process oil.
• the present embodiment an embodiment of the present invention (hereinafter, referred to as "the present embodiment") will be described in detail. It should be noted that the following embodiment is merely an example for explaining the present invention, and the present invention is not limited to the following embodiment. The present invention can be practiced with appropriate modifications within the scope of the gist of the present invention.
• Modified conjugated diene polymer The modified conjugated diene-based polymer of the present embodiment satisfies the following ⁇ Condition (i)> to ⁇ Condition (vi)>.
• ⁇ Condition (i)> The Mooney viscosity measured at 100° C. is 100 or more and 180 or less.
• ⁇ Condition (ii)> The Mooney relaxation coefficient measured at 100° C. is in the range of 0.10 to 0.40.
• ⁇ Condition (iii)> The glass transition temperature is -95°C to -45°C.
• ⁇ Condition (iv)> The silicon atom content is 100 ppm by mass or more based on the total amount of the modified conjugated diene polymer.
• the modified conjugated diene polymer of the present embodiment has excellent fuel-saving performance and processability, and even if it is a non-oil-extended product to which no process oil is added, it suppresses the decrease in thermal stability and has excellent bale formability.
• the modified conjugated diene polymer of the present embodiment has extremely excellent processability when vulcanized, and tends to achieve a particularly excellent balance between low hysteresis loss and wet skid resistance when vulcanized.
• the modified conjugated diene polymer of the present embodiment has excellent abrasion resistance, good strain dispersibility at 50° C., excellent repeated strain strength, and tends to have practically sufficient fracture properties when vulcanized.
• the modified conjugated diene polymer of this embodiment may be a homopolymer of a single conjugated diene compound, a polymer or copolymer of different types of modified conjugated diene compounds, or a copolymer of a conjugated diene compound and a vinyl aromatic compound.
• Conjugated diene compounds 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 effectively and reliably achieving the effects of this embodiment.
• These conjugated diene compounds may be used alone or in combination of two or more types.
• vinyl aromatic compounds include, but are not limited to, styrene, p-methylstyrene, ⁇ -methylstyrene, vinylethylbenzene, vinylxylene, vinylnaphthalene, and diphenylethylene.
• styrene is preferred from the viewpoint of effectively and reliably achieving the effects of this embodiment.
• vinyl aromatic compounds may be used alone or in combination of two or more types.
• Mooney Viscosity of Modified Conjugated Diene Polymer is an index showing the overall characteristics of a modified conjugated diene polymer, including information on the molecular weight, molecular weight distribution, branching degree, softener content, etc.
• the method for measuring the Mooney viscosity is specified in ISO289, and the measurement error due to the difference in the instrument is small, making it extremely effective in controlling the performance of the modified conjugated diene polymer.
• the modified conjugated diene polymer of the present embodiment has a Mooney viscosity (hereinafter also simply referred to as "Mooney viscosity” or “ML”) measured at 100°C of 100 or more, and from the viewpoints of steering stability, breaking strength, and abrasion resistance when the rubber composition for crosslinking is used for a tire, it is preferably 105 or more, and more preferably 115 or more.
• Mooney viscosity hereinafter also simply referred to as "Mooney viscosity” or "ML” measured at 100°C of 100 or more
• the upper limit is 180 or less, and from the viewpoints of molded bodies of various shapes such as sheet-like or block-like shapes, moldability and productivity of the rubber composition of this embodiment, and processability of a rubber composition blended with a filler or the like, it is preferably 170 or less, more preferably 160 or less, and even more preferably 150 or less.
• the moldability of the sheet-like or block-like molded body containing the modified conjugated diene polymer and the rubber composition tends to deteriorate.
• the Mooney viscosity is 100 or more, the blending of process oil is required to mold it into a veil, but in the modified conjugated diene polymer of this embodiment, as described below, a specific Mooney viscosity, Mooney relaxation rate, glass transition temperature, silicon atom content, and nitrogen atom content are specified.
• the modified conjugated diene polymer of this embodiment has a great feature in that it can be molded into a veil even if it is a polymer with a Mooney viscosity of 100 or more, which is usually difficult to mold into a veil without the addition of process oil.
• Mooney viscosity is specified to 180 or less, peeling of the modified conjugated diene polymer from the veil is suppressed, and good veil moldability is exhibited.
• the Mooney viscosity of the modified conjugated diene polymer is measured by the following method. First, a sample of the modified conjugated diene polymer formed into a plate shape by a pressure press is set in the device, and the sample is preheated at 100° C. for 1 minute. Then, the rotor is rotated at 2 rpm, and the torque is measured after 4 minutes, and the measured value is taken as the Mooney viscosity (ML (1+4) ). More specifically, it can be measured by the method described in the examples below.
• the Mooney viscosity of the modified conjugated diene polymer of the present embodiment can be controlled within the above-mentioned numerical range by adjusting the type, timing of use, and amount of the branching agent and coupling modifier, and the molecular weight, molecular weight distribution, and degree of branching of the modified conjugated diene polymer.
• Mooney relaxation rate (hereinafter also simply referred to as "Mooney relaxation rate” or “MSR") of the modified conjugated diene polymer of the present embodiment measured at 100°C is 0.40 or less, and from the viewpoint of processability of a rubber composition containing a filler or the like, it is preferably 0.35 or less, and more preferably 0.30 or less. On the other hand, it is 0.10 or more, and from the viewpoint of steering stability and breaking strength when the conjugated diene polymer of the present embodiment is used as a tire material, it is preferably 0.15 or more, and more preferably 0.20 or more.
• the Mooney relaxation rate is affected by the molecular weight, molecular weight distribution, degree of branching, and softener content of the modified conjugated diene polymer, and is an index showing the overall characteristics of the modified conjugated diene polymer.
• the MSR can be measured using a Mooney viscometer as follows.
• the Mooney relaxation rate is measured at a temperature of 100°C, and the sample is first preheated for 1 minute, then the rotor is rotated at 2 rpm, and the Mooney viscosity (ML (1+4) ) is measured from the torque 4 minutes later, after which the rotor rotation is immediately stopped.
• the torque is recorded in Mooney units every 0.1 seconds from 1.6 seconds to 5 seconds after the rotor has been stopped, and the slope of the straight line obtained by plotting the torque versus time (seconds) logarithmically is determined, and the absolute value of this value is the Mooney relaxation rate (MSR). More specifically, it can be measured by the method described in the Examples below.
• the Mooney relaxation rate of the modified conjugated diene polymer of the present embodiment can be controlled within the above-mentioned numerical range by adjusting the type, timing of use, and amount of the branching agent and coupling modifier, and the molecular weight, molecular weight distribution, and degree of branching of the modified conjugated diene polymer.
• the modified conjugated diene polymer of this embodiment has a glass transition temperature (hereinafter also referred to as "Tg") of -95°C or higher, preferably -78°C or higher, and more preferably -65°C or higher.
• Tg glass transition temperature
• a glass transition temperature of -95°C or higher results in excellent processability during vulcanization.
• the modified conjugated diene polymer of this embodiment has a glass transition temperature of -45°C or lower, preferably -55°C or lower, more preferably -58°C or lower, and even more preferably -60°C or lower.
• a glass transition temperature of -45°C or lower results in excellent breaking strength, abrasion resistance, and low hysteresis loss of a vulcanizate of the modified conjugated diene polymer.
• the glass transition temperature may be within a range that combines the upper and lower limits described above.
• the glass transition temperature of the modified conjugated diene polymer can be measured according to ISO 22768:2017. More specifically, a differential scanning calorimetry (DSC) measurement is performed while increasing the temperature within a predetermined temperature range, a DSC curve is recorded, and the peak top (inflection point) of the DSC differential curve is taken as the glass transition temperature. Specifically, it can be measured by the method described in the examples below.
• the silicon atom content is 100 ppm by mass or more based on the total amount of the modified conjugated diene polymer.
• the silicon atom content can be measured using 0.5 g of the modified conjugated diene polymer as a sample in accordance with JIS K 0101 44.3.1 using an ultraviolet-visible spectrophotometer (manufactured by Shimadzu Corporation under the trade name "UV-1800") and quantified by molybdenum blue absorptiometry.
• the content of silicon atoms is an index of the amount of coupling agent and modifier added in the modified conjugated diene polymer.
• the silicon content may be high in a modified conjugated diene polymer with a low molecular weight, and as the molecular weight increases, the amount of coupling agent and modifier added in the modified conjugated diene polymer decreases, so the silicon content tends to decrease.
• the interaction with a filler, such as silica added when preparing a composition tends to become stronger.
• the silicon atom content in the modified conjugated diene polymer of this embodiment is 100 mass ppm or more, preferably 130 mass ppm or more, and more preferably 150 mass ppm or more.
• the silicon atom content in the modified conjugated diene polymer of the present embodiment is preferably 500 ppm by mass or less, more preferably 400 ppm by mass or less, and even more preferably 350 ppm by mass or less.
• the silicon atom content tends to be controlled within the above range by adjusting the amount of modifier or coupling agent added and the reaction method.
• the modified conjugated diene polymer of the present embodiment has a nitrogen atom content of 50 ppm by mass or more based on the total amount of the modified conjugated diene polymer.
• the nitrogen atom content (hereinafter also referred to as "nitrogen content”) is the total amount of nitrogen atoms in the nitrogen-containing functional groups of the modified conjugated diene polymer, for example, in the initiation terminal, in the main chain, and at the terminal terminal.
• the nitrogen content of the modified conjugated diene polymer is 50 ppm by mass or more, preferably 60 ppm by mass or more, more preferably 70 ppm by mass or more, and even more preferably 80 ppm by mass or more, based on the total amount of the modified conjugated diene polymer, from the viewpoints of processability, balance between low hysteresis loss and wet skid resistance, abrasion resistance, and fracture properties. Also, from the viewpoint of processability, the nitrogen content is preferably 800 ppm by mass or less, more preferably 700 ppm by mass or less, even more preferably 600 ppm by mass or less, and even more preferably 500 ppm by mass or less.
• the nitrogen atom content can be measured by the oxidative combustion-chemiluminescence method (JIS-2609: Crude oil and crude oil products-Determination method for nitrogen content). More specifically, the nitrogen atom content can be measured by the method described in the Examples below.
• the nitrogen content tends to be controlled by adjusting the amount of the modifying agent added and the reaction method, and can be set to 50 mass ppm or more by this method.
• a method of polymerization using an organolithium compound having at least one nitrogen atom in the molecule as a polymerization initiator which will be described later, and a method of reacting a modified conjugated diene polymer having a nitrogen atom, which is obtained by a method of copolymerizing a monomer having at least one nitrogen atom in the molecule, with a modifying agent having at least one nitrogen atom in the molecule.
• examples of a method for obtaining a modified conjugated diene polymer having a nitrogen content of 500 ppm by mass or less include a method for controlling the molecular weight of the modified conjugated diene polymer chain so that it is not too small.
• the content of the antioxidant per 100 parts by mass of the modified conjugated diene polymer is 0.5 parts by mass or less.
• the antioxidant content (hereinafter also referred to as "antioxidant content”) is the total content of antioxidants contained in the modified conjugated diene polymer, and is added to ensure thermal stability.
• a modified conjugated diene polymer that generally has a high molecular weight and a high Mooney viscosity may have a high antioxidant content, and the amount of antioxidant added to the modified conjugated diene polymer tends to increase as the molecular weight increases.
• the modified conjugated diene polymer of this embodiment can be bale-molded with a reduced amount of antioxidant added by satisfying certain conditions.
• the content of the antioxidant relative to 100 parts by mass of the modified conjugated diene polymer is 0.5 parts by mass or less, preferably 0.45 parts by mass or less, more preferably 0.40 parts by mass or less, and even more preferably 0.35 parts by mass or less.
• thermal stability it is preferably 0.1 parts by mass or more, more preferably 0.2 parts by mass or more, and even more preferably 0.3 parts by mass or more.
• the content of the antioxidant can be measured by the HPLC analysis method described below.
• the modified conjugated diene polymer of the present embodiment has a weight average molecular weight measured by GPC measurement of preferably 45 ⁇ 10 4 or more, more preferably 50 ⁇ 10 4 or more, even more preferably 60 ⁇ 10 4 or more, even more preferably 65 ⁇ 10 4 or more, and even more preferably 70 ⁇ 10 4 or more.
• the weight average molecular weight measured by GPC measurement is 45 ⁇ 10 4 or more, the vulcanizate is more excellent in low hysteresis loss.
• the weight average molecular weight is preferably 250 ⁇ 10 4 or less, more preferably 200 ⁇ 10 4 or less, even more preferably 150 ⁇ 10 4 or less, and even more preferably 120 ⁇ 10 4 or less.
• the weight average molecular weight is 250 ⁇ 10 4 or less, the dispersibility of the filler in the vulcanizate is more excellent, and practically sufficient fracture properties tend to be obtained.
• the weight average molecular weight may be within a range that combines any of the above upper and lower limits.
• the weight average molecular weight of the modified conjugated diene polymer can be measured by the method described in the examples below.
• the modified conjugated diene polymer of the present embodiment has a number average molecular weight measured by GPC measurement of preferably 20 ⁇ 10 4 or more, more preferably 25 ⁇ 10 4 or more, and even more preferably 30 ⁇ 10 4 or more.
• the number average molecular weight may be 35 ⁇ 10 4 or more.
• the number average molecular weight measured by GPC measurement is 20 ⁇ 10 4 or more, the processability during vulcanization tends to be more excellent, and the vulcanizate tends to have more excellent low hysteresis loss properties.
• the number average molecular weight is preferably 100 ⁇ 10 4 or less, more preferably 90 ⁇ 10 4 or less, even more preferably 80 ⁇ 10 4 or less, and even more preferably 70 ⁇ 10 4 or less.
• the number average molecular weight is 20 ⁇ 10 4 or more, the dispersibility of the filler in the vulcanizate tends to be more excellent, and practically sufficient fracture properties tend to be obtained.
• the number average molecular weight may be within a range that combines any of the above upper and lower limits.
• the number average molecular weight of the modified conjugated diene polymer can be measured by the method described in the examples below.
• the ratio (Mw/Mn) of the weight average molecular weight (Mw) measured by GPC measurement to the number average molecular weight (Mn) measured by GPC measurement is preferably 1.4 or more, more preferably 1.5 or more, even more preferably 1.6 or more, and still more preferably 1.7 or more, from the viewpoints of processability during vulcanization, abrasion resistance and breaking strength of the vulcanizate.
• the upper limit of the molecular weight distribution is not particularly limited, but is generally preferably 2.5 or less, more preferably 2.2 or less, even more preferably 2.0 or less, and still more preferably 1.9 or less.
• the molecular weight distribution of the modified conjugated diene polymer can be controlled within the above-mentioned numerical range by adjusting the polymerization conditions such as the type and amount of monomer, polymerization initiator, and polar compound, polymerization time, polymerization temperature, the amount and type of coupling modifier added, and when two or more types are used, the combination thereof.
• microstructure of modified conjugated diene polymer The microstructure of the modified conjugated diene polymer (the amount of bound vinyl aromatic compounds, the amount of bound conjugated diene compounds, and the proportion of vinyl bonds in the bound conjugated diene compounds) affects the glass transition temperature of the modified conjugated diene polymer. Therefore, the amount of vinyl aromatic compounds and the amount of vinyl bonds have a preferred range from the viewpoint of controlling the glass transition temperature.
• the amount of bound vinyl aromatic compounds is not particularly limited, but is preferably 1% by mass or more and 40% by mass or less, more preferably 1% by mass or more and 36% by mass or less, even more preferably 1% by mass or more and 30% by mass or less, even more preferably 2% by mass or more and 29% by mass or less, even more preferably 3% by mass or more and 28% by mass or less, and particularly preferably 5% by mass or more and 27% by mass or less, based on the entire modified conjugated diene polymer.
• the vulcanizate of the modified conjugated diene polymer tends to be more excellent in fracture strength, abrasion resistance, and low hysteresis loss.
• the amount of the bound vinyl aromatic compound increases, the Tg of the modified conjugated diene polymer tends to increase, whereas when the amount of the bound vinyl aromatic compound decreases, the Tg tends to decrease.
• the "amount of bound vinyl aromatic compound” means the content of the portion derived from the aromatic vinyl compound used as a monomer.
• modified conjugated diene polymers containing vinyl aromatic compounds when the vinyl bond amount in the conjugated diene bond unit or the content of vinyl aromatic compounds is set low, the Tg of the modified conjugated diene polymer decreases, and the abrasion resistance and low hysteresis tend to increase when vulcanized, so there is a need to design a polymer having such a structure.
• setting the vinyl bond amount or the content of vinyl aromatic compounds low may have a negative effect on the moldability when forming a block-shaped veil molded body and the processability when forming a vulcanized product.
• the present inventors have found that by using the modified conjugated diene polymer of the present embodiment, the bale molding is excellent even if the modified conjugated diene polymer is not oil-extended. Therefore, in the design of the microstructure of the non-oil-extended product, the constraint that the vinyl bond amount and the vinyl aromatic compound content cannot be reduced is alleviated, and it has become possible to set the glass transition temperature low.
• the amount of the bound conjugated diene compound is not particularly limited, but is preferably 60% by mass or more and 99% by mass or less, more preferably 64% by mass or more and 99% by mass or less, even more preferably 70% by mass or more and 99% by mass or less, even more preferably 71% by mass or more and 98% by mass or less, even more preferably 72% by mass or more and 97% by mass or less, and particularly preferably 73% by mass or more and 95% by mass or less, based on the entire modified conjugated diene polymer.
• the vulcanizate of the modified conjugated diene polymer tends to have even better fracture strength, abrasion resistance, and low hysteresis loss.
• the "amount of bound conjugated diene compound” means the content of the portion derived from the conjugated diene compound as a monomer.
• the 1,2-vinyl bond content (hereinafter also simply referred to as "vinyl bond amount”) relative to the total mass of the modified conjugated diene polymer is not particularly limited, but is preferably 11.0 mol% to 60.0 mol%, more preferably 11.0 mol% to 45.0 mol%, even more preferably 12.0 mol% to 35.0 mol%, still more preferably 13.0 mol% to 34.0 mol%, still more preferably 14.0 mol% to 33.0 mol%, and particularly preferably 15.0 mol% to 30.0 mol%.
• the modified conjugated diene polymer has improved linearity of the structure of the conjugated diene portion and stronger entanglement between polymer chains, so that the fracture strength and abrasion resistance tend to be even more excellent. Furthermore, when the vinyl bond amount is within the above range, the vulcanizate tends to have even more excellent low hysteresis loss properties. In addition, an increase in the amount of vinyl bonds increases Tg, whereas a decrease in the amount of vinyl bonds decreases Tg.
• the term "amount of vinyl bonds in a bonded conjugated diene” refers to the proportion of a portion having a vinyl bond among a portion derived from a conjugated diene compound (hereinafter referred to as "bonded conjugated diene").
• the shrinkage factor (g') is a relative representation of the molecular size of the target polymer, and is an index of the ratio of the molecular size of the target polymer to the molecular size of a linear polymer with the same absolute molecular weight as the target polymer. In other words, if the degree of branching of a polymer is high, its size will be relatively small, and therefore the shrinkage factor (g') will tend to be small.
• the shrinkage factor (g') is defined as the ratio of the intrinsic viscosity [ ⁇ ] of the target polymer to the intrinsic viscosity [ ⁇ 0 ] of a linear polymer having the same absolute molecular weight as the target polymer ([ ⁇ ]/[ ⁇ 0 ]).
• M is the absolute molecular weight. Therefore, the shrinkage factor (g') and the degree of branching (Bn) can be obtained by measuring the absolute molecular weight and intrinsic viscosity of a target polymer by a GPC-light scattering method with a viscosity detector.
• the calculated degree of branching (Bn) accurately represents the number of polymer chains that are directly or indirectly bonded to each other with respect to the longest polymer main chain.
• absolute molecular weight means the molecular weight measured by the light scattering method.
• polymers with branches tend to have smaller molecular size compared to linear polymers with the same absolute molecular weight. Therefore, the molecular weight of polymers with branched structures tends to be underestimated in the GPC measurement method, which is a method of determining the molecular weight by screening the polymer according to molecular size and comparing it relative to a standard polystyrene sample.
• the light scattering method measures the molecular weight by directly observing the molecules. Therefore, the light scattering method can accurately measure the molecular weight without being affected by the polymer structure or the interaction with the column packing material.
• the absolute molecular weight can be measured by the method described in the examples below.
• intrinsic viscosity ideally means the viscosity [ ⁇ ] calculated by the following formula (I).
• ⁇ 1 represents the viscosity when the target polymer is dissolved in a solvent at a concentration c
• ⁇ 2 represents the viscosity of the solvent.
• the intrinsic viscosity is a value measured by the method described in the Examples section below.
• the above shrinkage factors represent the rate of reduction in molecular size and do not accurately represent the branched structure of the polymer.
• the branching degree (Bn) of the modified conjugated diene polymer is calculated using the value of the shrinkage factor (g') at each absolute molecular weight of the modified conjugated diene polymer.
• the calculated "branching degree (Bn)" accurately represents the number of polymers that are directly or indirectly bonded to each other in the longest main chain structure.
• the calculated branching degree (Bn) is an index that expresses the branching structure of a modified conjugated diene polymer. For example, in the case of a typical four-branched star polymer (four polymer chains connected to the center), two arms of the polymer chain are bonded to the longest highly branched main chain structure, and the branching degree (Bn) is evaluated as 2.
• the modified conjugated diene polymer of this embodiment preferably has a branching degree (Bn) of 2 or more, which means that the modified conjugated diene polymer has a star polymer structure with four branches similar to a star polymer structure.
• branching refers to a polymer that is formed by directly or indirectly bonding with another polymer.
• branching degree (Bn) refers to the number of polymers that are directly or indirectly bonded to each other in the longest main chain structure.
• the modified conjugated diene polymer of this embodiment has excellent processability when vulcanized, and when vulcanized, has excellent abrasion resistance and breaking strength.
• the branching degree (Bn) of the modified conjugated diene polymer of this embodiment is 2 or more, the increase in viscosity when vulcanized due to an increase in absolute molecular weight is significantly suppressed. Therefore, for example, it becomes possible to mix sufficiently with silica, etc. in the kneading process, and it becomes possible to disperse silica around the modified conjugated diene polymer.
• the modified conjugated diene polymer it is possible to improve abrasion resistance and fracture strength by setting the molecular weight large, and also to disperse silica around the polymer by sufficient kneading, allowing the functional groups to act and/or react. This makes it possible to obtain a polymer with low hysteresis loss and wet skid resistance that are sufficient for practical use.
• the absolute molecular weight of the modified conjugated diene polymer can be measured by the method described in the examples below.
• the degree of branching (Bn) of the modified conjugated diene polymer of the present embodiment is preferably 2 or more, more preferably 3 or more, even more preferably 4 or more, still more preferably 5 or more, particularly preferably 6 or more, and even more preferably 8 or more.
• a modified conjugated diene polymer having a degree of branching (Bn) within this range tends to have excellent processability and bale moldability when made into a vulcanizate.
• the upper limit of the branching degree (Bn) is not particularly limited and may be equal to or higher than the detection limit, but is preferably 84 or less, more preferably 80 or less, even more preferably 60 or less, particularly preferably 40 or less, and even more preferably 20 or less.
• the modified conjugated diene polymer of the present embodiment has a degree of branching (Bn) of 84 or less, and therefore tends to have excellent abrasion resistance when vulcanized.
• the degree of branching of the modified conjugated diene polymer can be controlled to 2 or more by combining the amount of the branching agent and the amount of the terminal coupling agent. Specifically, the degree of branching can be controlled by the number of functional groups of the branching agent, the amount of the branching agent added, the timing of adding the branching agent, and the number of functional groups of the coupling agent or nitrogen atom-containing modifier, and the amount of the coupling agent or nitrogen atom-containing modifier added. More specifically, this is described in the method for producing the modified conjugated diene polymer described below.
• the abrasion resistance and breaking strength of a polymer tend to be better as the absolute molecular weight of the polymer increases.
• the absolute molecular weight of a polymer with a low degree of branching is increased, polymer particles tend to peel off easily from the surface of the veil, and veil moldability deteriorates.
• the viscosity during vulcanization increases significantly, and processability during vulcanization tends to deteriorate significantly.
• the modified conjugated diene polymer of the present embodiment preferably has a modifying group.
• the term "modifying group" refers to a functional group that has affinity or bonding reactivity with the filler, and includes functional groups that contain a nitrogen atom.
• the modified conjugated diene polymer of the present embodiment has such a modifying group, which further improves the interaction with the filler, and therefore when the modified conjugated diene polymer is made into a composition containing the modified conjugated diene polymer and a filler, the breaking strength of the composition is further improved.
• the modified conjugated diene polymer of the present embodiment preferably has a modifying group having a nitrogen atom, and more preferably has a modifying group having a nitrogen atom and a silicon atom. It is not necessary for one modifying group or coupling modifier to contain both a nitrogen atom and a silicon atom, and a modifying group containing only one of them or a coupling modifier having a modifying group may be combined so that the polymer contains both nitrogen and silicon.
• the "modification rate” refers to the content, expressed in mass %, of a modified conjugated diene polymer component having a specific functional group having affinity or binding reactivity with a filler relative to the total amount of the conjugated diene polymer mixture, in the case where a mixture of a modified conjugated diene polymer and an unmodified conjugated diene polymer is obtained by modifying a conjugated diene polymer with a coupling modifier using a nitrogen-containing lithium compound as an initiator, which will be described later.
• the “modification rate” refers to the mass ratio of the modified conjugated diene polymer containing a nitrogen atom relative to the total amount of the conjugated diene polymer mixture.
• the term “conjugated diene-based polymer” encompasses unmodified conjugated diene-based polymers and modified conjugated diene-based polymers.
• the "conjugated diene polymer” means an unmodified conjugated diene polymer.
• the modification rate is the mass ratio of the modified 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 modified conjugated diene polymer of this embodiment preferably has at least a nitrogen atom at the terminal, and more preferably is modified with a functional group containing a nitrogen atom and a silicon atom in addition to the nitrogen atom at the terminal.
• a modified conjugated diene polymer has better processability when blended with a filler or the like to form a rubber composition, and tends to have better abrasion resistance, breaking strength, and low hysteresis loss when the rubber composition is vulcanized.
• the modification rate of the modified conjugated diene polymer of this embodiment is preferably 85 mass% or more, more preferably 88 mass% or more, even more preferably 89 mass% or more, even more preferably 90 mass% or more, and even more preferably 91 mass% or more, based on the total amount of the modified conjugated diene polymer.
• the upper limit of the modification rate is not particularly limited, but may be 100 mass%, 98 mass% or less, 96 mass% or less, or 95 mass% or less.
• those with a higher modification rate tend to have better low hysteresis loss properties.
• the modification rate can be measured by chromatography that can separate functional group-containing modified components from non-modified components.
• chromatography examples include a method in which a gel permeation chromatography column is filled 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 (column adsorption GPC method).
• the modification rate can be obtained by calculating the amount of adsorption to the silica-based column from the difference between a chromatogram obtained by measuring a sample solution containing the sample and low-molecular-weight internal standard polystyrene on a polystyrene-based gel column and a chromatogram obtained by measuring the sample solution on a silica-based column.
• the modification rate can be measured by the method described in the Examples below.
• the modification rate can be controlled within the above-mentioned numerical range by adjusting the amount of the coupling modifier added and the reaction method between the modified conjugated diene compound and the modifier.
• a method of polymerization using an organolithium compound having at least one nitrogen atom in the molecule as a polymerization initiator as described below 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 may be combined.
• the modified conjugated diene polymer of the present embodiment has a nitrogen atom at at least one terminal and at least one branched chain having a star structure, the branched chain having a star structure has a portion derived from a vinyl monomer containing an alkoxysilyl group or a halosilyl group described below, and the portion derived from the vinyl monomer containing an alkoxysilyl group or a halosilyl group preferably has a further main chain branched structure and has a coupling structure centered on a nitrogen-containing alkoxysilane substituent.
• the modified conjugated diene polymer chain is bonded to the modifier refers to the state of a compound formed by bonding the polymer chain to a so-called coupling agent (modifier) in the polymer production process. Therefore, the structure of the "modifier” (also written as “modifier residue") in the polymer is different from the initial structure of the modifier, since the leaving group is no longer present in the modifier before the reaction and the polymer chain is bonded.
• the modifier (residue) contained in the modified conjugated diene polymer is a structural unit of the modified conjugated diene polymer that is bonded to the modified conjugated diene polymer chain, and is, for example, a structural unit derived from the modifier that is generated by reacting the conjugated diene polymer described later with the modifier.
• a modified conjugated diene polymer containing a nitrogen atom and a silicon atom in the modifier contains both a nitrogen atom and a silicon atom, and therefore tends to have a stronger interaction with a filler, such as silica, added when the polymer is made into a composition, compared to a polymer containing only one of the two.
• the modified conjugated diene polymer chain has a nitrogen atom at at least one end and at least one branched chain having a star-shaped structure
• the branched chain having a star-shaped structure has a portion derived from a vinyl monomer containing an alkoxysilyl group or a halosilyl group
• the portion derived from the vinyl monomer containing an alkoxysilyl group or a halosilyl group has a further main chain branched structure and has a coupling structure centered on a nitrogen-containing alkoxysilane substituent.
• the structural unit derived from the modified conjugated diene polymer of the present embodiment is a constituent unit of the modified conjugated diene polymer, and has, for example, a portion derived from a vinyl monomer containing an alkoxysilyl group or a halosilyl group with respect to a modified conjugated diene polymer chain having a nitrogen atom introduced at one end derived from an organolithium compound having at least one nitrogen atom in the molecule described below, and the portion derived from the vinyl monomer containing an alkoxysilyl group or a halosilyl group has a further main chain branched structure and may be obtained by reacting the modified conjugated diene polymer with a modifier.
• the modified conjugated diene polymer chain having a nitrogen atom at its terminal has a portion derived from a vinyl monomer containing an alkoxysilyl group or a halosilyl group, and in the portion derived from the vinyl monomer containing an alkoxysilyl group or a halosilyl group, a further main chain branch structure is formed, and it is preferable that the portion has a star-shaped branch structure bonded to one modifier, and more preferably, the number of alkoxysilane residues of the modifier is greater than the number of conjugated diene polymer chains bonded to the modifier.
• the conjugated diene polymer chain preferably has a nitrogen atom in at least one conjugated diene polymer chain.
• it is a conjugated diene polymer chain having a functional group containing a nitrogen atom at any position, and the position of the functional group may be at the terminal or in the middle of the main chain.
• the conjugated diene polymer chain having a nitrogen atom can be obtained, for example, by a method of polymerization using an organolithium compound having at least one nitrogen atom in the molecule described later as a polymerization initiator, or a method of copolymerizing a monomer having at least one nitrogen atom in the molecule.
• the modified conjugated diene polymer of this embodiment or the conjugated diene polymer described later may be one in which all or part of the double bonds are converted to saturated hydrocarbons by further hydrogenating in an inert solvent.
• the heat resistance and weather resistance are improved, deterioration of the product when processed at high temperatures can be prevented, and the dynamic performance as rubber tends to be improved. As a result, it exhibits even better performance in various applications such as automobile applications.
• the hydrogenation rate of the unsaturated double bonds based on the conjugated diene compound can be arbitrarily selected according to the purpose and is not particularly limited. When used as a vulcanizate, it is preferable that the double bonds of the conjugated diene part remain partially.
• the hydrogenation rate of the conjugated diene part in the conjugated diene polymer is preferably 3.0% or more and 70% or less, more preferably 5.0% or more and 65% or less, and even more preferably 10% or more and 60% or less.
• selective hydrogenation of the vinyl group tends to improve the heat resistance and dynamic performance.
• the hydrogenation rate can be determined by a nuclear magnetic resonance (NMR) device.
• a vinyl monomer containing an alkoxysilyl group or a halosilyl group used in constructing the "main chain branched structure” is referred to as a "branching agent".
• the branching agent it is preferable to use a vinyl monomer containing an alkoxysilyl group or a halosilyl group represented by the following formula (1) or (2). That is, it is preferable that the "main chain branch structure" is composed of an atomic group derived from a vinyl monomer containing an alkoxysilyl group or a halosilyl group represented by the following formula (1) or (2).
• R 1 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, which may partially have a branched structure.
• R 2 to R 3 each independently represent an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, which may partially have a branched structure. When a plurality of R 1 to R 3 are present, each is independent of each other.
• X1 independently represents a halogen atom.
• m represents an integer of 0 to 2
• n represents an integer of 0 to 3
• l represents an integer of 0 to 3. (m+n+l) represents 3.
• R 4 to R 7 each independently represent an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, which may partially have a branched structure. When a plurality of R 4 to R 7 are present, they are each independent.
• X 2 to X 3 each independently represent a halogen atom.
• m is an integer of 0 to 2
• n is an integer of 0 to 3
• 1 is an integer of 0 to 3.
• (m+n+l) represents 3.
• a represents an integer of 0 to 3
• b represents an integer of 0 to 2
• c represents an integer of 0 to 3.
• (a+b+c) represents an integer of 3.
• the modified conjugated diene polymer of this embodiment has a coupling structure centered on a nitrogen-containing alkoxysilane substituent, in which the nitrogen-containing alkoxysilane modifier residue has at least four silicon atoms and an alkoxy group and/or a hydroxy group, and a modified conjugated diene polymer chain having a main chain branched structure is bonded to the silicon atom, and it is preferable that the number of the alkoxy groups and/or the hydroxy groups in the modifier residue described below is greater on average than the number of the silicon atoms.
• the modified conjugated diene polymer of the present embodiment preferably has a silicon atom in the modifier residue.
• the modifier described below contains a silicon atom, resulting in a modified conjugated diene polymer having a structural unit derived from the modifier.
• the modified conjugated diene polymer of the present embodiment preferably has a silicon atom at any position.
• the silicon atom is preferably bonded to the end of the conjugated diene polymer chain or in the middle of the main chain as a silicon atom-containing functional group, or is preferably contained in a modifier residue. It is more preferable that at least one silicon atom possessed by this modified conjugated diene polymer constitutes an alkoxysilyl group or a silanol group having 1 to 20 carbon atoms. This tends to strengthen the interaction with a filler, such as silica, added when making a vulcanizate. In addition, from the viewpoint of the possibility of generating hydrogen halide by reaction with air, it is preferable that the modified conjugated diene polymer does not contain a halogen.
• At least one end of the 8 or more conjugated diene polymer chains is bonded to a silicon atom of the modifier residue. This tends to make the effect of this embodiment more pronounced.
• the ends of multiple conjugated diene polymer chains may be bonded to one silicon atom.
• an end of a conjugated diene polymer chain and an alkoxy group or hydroxyl group having 1 to 20 carbon atoms may be bonded to one silicon atom, and as a result, the one silicon atom may constitute an alkoxysilyl group or silanol group having 1 to 20 carbon atoms.
• hydrogen halide may be generated by reaction with air or moisture, it is preferable that the modifier residue does not have a halogen.
• a central branch point here refers to an assembly (atomic group) having a substituent containing an atom derived from a coupling modifier or a nitrogen atom derived from a modifier, and does not mean a single atom.
• a typical central branch point is an assembly having an alkoxysilyl group separated by 1 to 5 carbons, preferably 2 to 3 carbons, from an amino group.
• the modified conjugated diene polymer having a star-shaped polymer structure is a conjugated diene polymer having a three or more branched star-shaped polymer structure constructed by constructing a branched structure portion derived from a main chain branched structure portion, continuing polymerization to increase the molecular weight, and then modifying the polymer with a coupling modifier having three or more functionalities.
• a modified conjugated diene polymer has a portion derived from a vinyl monomer containing an alkoxysilyl group or a halosilyl group in at least one branched chain of the star-shaped structure.
• the "star polymer structure" can be formed by adjusting the number of functional groups of the modifier and the amount of the modifier added, and the "main chain branched structure” can be controlled by adjusting the number of functional groups of the branching agent, the amount of the branching agent added, and the timing of the addition of the branching agent.
• the modified conjugated diene polymer of this embodiment preferably contains a structure having a nitrogen atom-containing group in its star-shaped branched structure portion, which is represented by any one of the following general formulas (5-1) to (5-4), (7-1) to (7-2), (8), and (9-1) to (9-2).
• R is a divalent or higher hydrocarbon group, or a divalent or higher organic group having at least one polar group selected from polar groups containing oxygen such as ether, epoxy, and ketone, polar groups containing sulfur such as thioether and thioketone, and polar groups containing nitrogen such as tertiary amino and imino groups.
• 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 24 and R 27 are hydrocarbon groups having 1 to 10 carbon atoms, and R 24 and R 27 may be the same or different.
• R 25 and R 28 are each a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and R 25 and R 28 may be the same or different.
• P 3 and P 4 are polymer chains, and are either fork-shaped portions [A] having a main chain branched structure, or linear polymer chains having no branched structure.
• R 26 is a hydrocarbon group having 1 to 10 carbon atoms, or a structure represented by any one of the following formulas (6-1) to (6-3).
• R 24 , R 25 and R 26 may be bonded to each other to form a cyclic structure.
• R 26 when R 26 is a hydrocarbon group, it may be a cyclic structure bonded to R. In the case of the cyclic structure, the N bonded to R 26 and R may be directly bonded to each other.
• f is an integer of 1 or more
• g is 0 or an integer of 1 or more.
• R 29 and R 30 are defined similarly to R 24 and R 25 in the formulae (5-1) to (5-4), respectively, and in the formulae (6-1) to (6-3), P 5 is defined similarly to P 3 and P 4 in the formulae (5-1) to (5-4). R 29 and R 30 may be the same or different.
• P 6 and P 7 are polymer chains, and are either fork-shaped portions [A] having a main chain branched structure or linear polymer chains having no branched structure.
• P 6 s and P 7 s may be the same or different from each other.
• R 33 and R 34 each independently represent an alkyl group or a hydrocarbyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms;
• R 35 represents an alkylene group having 1 to 10 carbon atoms;
• R 36 represents an alkylene group having 1 to 20 carbon atoms.
• h represents an integer of 1 to 3
• i represents an integer of 1 to 3
• j represents an integer of 1 or 2
• (h+i) and (h+j) represent integers of 3 or more.
• P 8 , P 9 and P 10 are polymer chains, and are either forked portions [A] having a main chain branched structure or linear polymer chains having no branched structure.
• P 8 , P 9 and P 10 may be the same or different from each other.
• R 40 to R 42 each independently represent an alkyl group or hydrocarbyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms
• R 43 to R 45 each independently represent an alkylene group having 1 to 20 carbon atoms.
• m, n, and l each independently represent an integer of 1 to 3, and (m+n+l) represents an integer of 3 or greater.
• P 11 to P 14 are polymer chains, and are fork-shaped portions [A] having a main chain branched structure portion or linear polymer chains having no branched structure.
• P 11 and P 12 may be the same or different from each other.
• R 46 to R 48 each independently represent a single bond or an alkylene group having 1 to 20 carbon atoms
• R 49 and R 51 each independently represent an alkyl group or a hydrocarbyl group having 1 to 20 carbon atoms
• R 53 and R 56 each independently represent an alkylene group having 1 to 20 carbon atoms
• R 55 represents an alkyl group or a trialkylsilyl group having 1 to 20 carbon atoms, which may be substituted with an organic group containing S, O, or N and not having active hydrogen, and which may have an unsaturated bond, and which may be the same or different.
• o represents an integer of 1 to 3
• p represents 1 or 2
• t represents an integer of 1 to 3.
• R 46 to R 56 When there are multiple of each of R 46 to R 56 , o, p, and t, they are independent and may be the same or different.
• q is an integer of 0 to 6
• r is an integer of 0 to 6
• s is an integer of 0 to 6
• (q+r+s) is an integer of 4 to 10.
• 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 oxygen atoms, nitrogen atoms, silicon atoms, sulfur atoms, and phosphorus atoms and having no active hydrogen atoms.
• A is preferably represented by any one of the following general formulas (I) to (IV).
• B 1 represents a single bond or a hydrocarbon group having 1 to 20 carbon atoms, and u represents an integer of 1 to 10. When a plurality of B 1 are present, each B 1 is independent.
• B2 represents a single bond or a hydrocarbon group having 1 to 20 carbon atoms
• B3 represents an alkyl group having 1 to 20 carbon atoms
• u represents an integer of 1 to 10.
• B 4 represents a single bond or a hydrocarbon group having 1 to 20 carbon atoms, and u represents an integer of 1 to 10. When a plurality of B 4s are present, each B 4 is independent.
• B 5 represents a single bond or a hydrocarbon group having 1 to 20 carbon atoms, and u represents an integer of 1 to 10. When a plurality of B 5s are present, each B 5 is independent.
• the molded article of the present embodiment is a molded article containing the conjugated diene-based polymer of the present embodiment described above. From the viewpoint of handling, the molded article is preferably in the form of a sheet or a block.
• the size and thickness of the sheet-like or block-like molded product are not particularly limited, but examples thereof include a sheet-like molded product having a thickness of about 1 cm, and a rectangular or cubic block-like molded product having a size of 1,000 cm3 .
• the molded product of this embodiment is preferably a block-shaped molded product, and the shape of the block is preferably a roughly rectangular parallelepiped, and more preferably a block-shaped (bale) molded product of 1,000 cm3 or more. In addition, a rectangular parallelepiped bale weighing 17.5 kg to 35 kg is even more preferable.
• a preferred molding method is to prepare crumbs having a specific surface area of 0.7 m 2 / g to 3.2 m 2 /g and then compression mold the crumbs. From the viewpoint of moldability, it is preferred to further carry out a step of sieving the crumbs before molding. When the crumbs are compression molded, the crumbs are in close contact with each other, so the specific surface area of the molded body is smaller than that of the crumbs.
• the adhesion of the crumbs during compression molding can be adjusted by the molecular weight, composition, and structure of the conjugated diene polymer, the softener component composition, and the temperature and pressure during compression.
• the molecular weight of the conjugated diene polymer when it is desired to increase the adhesion of the crumbs and decrease the specific surface area of the veil, it is preferable to decrease the molecular weight of the conjugated diene polymer, increase the amount of the softener component, and increase the temperature and pressure during compression.
• the specific surface area of the molded article of this embodiment is preferably 0.005 to 0.05 m 2 /g, and more preferably 0.01 to 0.04 m 2 /g from the viewpoint of film packaging.
• a specific surface area of 0.005 m 2 /g or more of the molded article suppresses the expansion of the bale, and a specific surface area of 0.05 m 2 /g or less of the molded article is preferable because it reduces the peeling of crumbs from the molded article.
• the specific surface area of the molded body can be determined by the BET method. Generally, since the specific surface area of a large-sized molded body may vary depending on the location, it is preferable to collect from near the center of the molded body.
• the crumbs are preferably sieved according to particle size and then mixed in an appropriate ratio. If the specific surface area of the molded body formed using the crumbs after desolvation exceeds the upper limit of the above range, it is preferable to increase the composition of large crumbs and decrease the composition of small crumbs among the sieved crumbs, and if it does not reach the lower limit, it is preferable to decrease the composition of large crumbs and increase the composition of small crumbs.
• the molding compression pressure for the molded body is preferably 3 MPa to 30 MPa, and more preferably 10 MPa to 20 MPa.
• the molding compression pressure is 30 MPa or less, the equipment can be designed compactly and installation efficiency is good.
• the molding compression pressure is 3 MPa or more, moldability is good.
• moldability is good, the surface of the molded body is smooth, there is no peeling of the polymer after the molding process, and expansion after molding tends to be suppressed.
• the temperature of the conjugated diene polymer or the rubber composition containing the conjugated diene polymer during molding is preferably 30 to 120°C, and more preferably 50 to 100°C from the viewpoints of reducing residual solvent and suppressing thermal degradation.
• a molding temperature of 30° C. or higher provides good moldability, while a molding temperature of 120° C. or lower is preferred because gel formation due to thermal degradation of the rubber composition can be suppressed.
• the higher the temperature and pressure during molding the smaller the specific surface area of the bale.
• the pressure retention time during compression is preferably 3 to 30 seconds, more preferably 5 to 20 seconds. When the pressure retention time during compression is 30 seconds or less, production efficiency is good, and when it is 5 seconds or more, moldability is good.
• a resin film In order to prevent the molded bodies from sticking to each other, it is preferable to wrap them in a resin film (wrapping sheet).
• the type of resin that can be used for the film includes, for example, polyethylene, ethylene copolymer resin, polystyrene, high impact polystyrene, and PET (polyethylene terephthalate). From the viewpoints of ease of handling during transportation of the molded article and preventing condensation from forming in the gap between the packaging sheet and the bale, it is preferable that the packaging sheet has good adhesion.
• the molded article of the present embodiment is used, for example, for storage in a container for transportation. If the expansion rate of the molded article one day after molding is less than 5%, the molded article has good storage properties in the container, which is preferable.
• the method for producing a modified conjugated diene polymer of the present embodiment is a method for producing a modified conjugated diene polymer of the present embodiment, A step of polymerizing at least a conjugated diene compound in the presence of an organolithium compound having at least one nitrogen atom in the molecule; a branching step for obtaining a branched modified conjugated diene polymer having a main chain branched structure using a branching agent (hereinafter, these steps may be collectively referred to as a polymerization branching step); having In the step of coupling the branched modified conjugated diene polymer with a coupling agent and/or in the step of modifying the branched modified conjugated diene polymer with a modifying agent having a nitrogen atom-containing group, the coupling agent and/or the modifying agent are added in excess.
• the step of coupling using a coupling agent and/or the step of modifying with a modifying agent having a nitrogen atom-containing group may be a step of adding a coupling modifying agent.
• the polymerization reaction of the conjugated diene compound and the aromatic vinyl compound is preferably a growth reaction caused by a living anionic polymerization reaction, which makes it possible to obtain a conjugated diene polymer having an active end.
• a branching agent when added, the conjugated diene polymer reacts with the branching agent efficiently.
• the manufacturing method of this embodiment has a coupling step described below, it tends to be possible to carry out a highly efficient reaction.
• Polymerization reaction modes include, but are not limited to, batch and continuous polymerization reaction modes.
• one or more connected reactors can be used.
• a tank type or a tube type equipped with an agitator is used.
• the monomer, the inert solvent described below, and the polymerization initiator described below are continuously fed to the reactor, a polymer solution containing a polymer is obtained in the reactor, and the polymer solution is continuously discharged.
• a batch reactor for example, a tank-type reactor equipped with an agitator is used.
• the monomer, the inert solvent described below, and the polymerization initiator described below are fed, and if necessary, the monomer is added continuously or intermittently during the polymerization, and a polymer solution containing the polymer is obtained in the reactor, and the polymer solution is discharged after the polymerization is completed.
• the manufacturing method of this embodiment from the viewpoint of being able to obtain a conjugated diene-based polymer having a high percentage of active ends, it is preferable to carry out the polymerization reaction in a continuous polymerization reaction mode in which the polymer can be continuously discharged and subjected to the next reaction in a short period of time.
• the polymerization branching step in the method for producing a conjugated diene polymer of the present embodiment is a step of obtaining a conjugated diene polymer having a branched structure by polymerizing at least a conjugated diene compound and, if necessary, a vinyl aromatic compound using an organolithium compound having at least one nitrogen atom in the molecule as described below as a polymerization initiator, and adding a branching agent while polymerizing at least a conjugated diene compound and, if necessary, a vinyl aromatic compound. Therefore, in the polymerization branching step, the polymerization reaction of at least the conjugated diene compound and the aromatic vinyl compound is the main reaction before the branching agent is added, and the branching reaction starts after the branching agent is added.
• conjugated diene compound and vinyl aromatic compound which are the monomers used in the polymerization branching step
• at least one of the above-mentioned conjugated diene compounds and at least one of the above-mentioned vinyl aromatic compounds may be used.
• the above-mentioned conjugated diene compound or the above-mentioned vinyl aromatic compound may be a derivative substituted to have at least one nitrogen atom in the molecule.
• a predetermined polymerization initiator is used.
• the polymerization initiator may be an organolithium compound, and preferably an organolithium compound having at least one nitrogen atom in the molecule is used.
• the organolithium compound includes an organomonolithium compound, and may be used in combination with other polymerization initiators.
• examples of the organomonolithium compound include, but are not limited to, 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 organomonolithium compound used as a polymerization initiator is preferably determined depending on the molecular weight of the target conjugated diene polymer or modified conjugated diene polymer.
• the amount of monomer such as conjugated diene compound used relative to the amount of polymerization initiator used tends to relate to the degree of polymerization, i.e., to the number average molecular weight and/or weight average molecular weight. Therefore, in order to increase the molecular weight, it is advisable to adjust the amount of polymerization initiator to a smaller amount, and in order to decrease the molecular weight, it is advisable to adjust the amount of polymerization initiator to a larger amount.
• the organic monolithium compound is preferably an alkyllithium compound having a substituted amino group, or a substituted aminolithium compound, from the viewpoint that it is used as one method for introducing nitrogen atoms into a conjugated diene polymer.
• a conjugated diene polymer having a nitrogen atom resulting from an amino group at the polymerization initiation terminal is obtained.
• the substituted amino group is an amino group that does not have active hydrogen or has a structure in which the active hydrogen is protected.
• the organolithium compound having at least one nitrogen atom in the molecule as the polymerization initiator includes an organolithium compound represented by any of the following general formulas (1) to (5).
• R 10 and R 11 each independently represent at least one selected from the group consisting of an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 14 carbon atoms, an aralkyl group having 6 to 20 carbon atoms, and a protecting group; R 10 and R 11 may be bonded together to form a cyclic structure together with the adjacent nitrogen atom, in which case R 10 and R 11 represent an alkyl group having 5 to 12 carbon atoms, which may have an unsaturated bond or a branched structure in a portion thereof.
• the protecting group is an alkyl-substituted silyl group.
• R 12 and R 13 each independently represent at least one selected from the group consisting of an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 14 carbon atoms, an aralkyl group having 6 to 20 carbon atoms, and a protecting group; R 12 and R 13 may be bonded together to form a cyclic structure together with the adjacent nitrogen atom, in which case R 12 and R 13 represent an alkyl group having 5 to 12 carbon atoms, which may have an unsaturated bond or a branched structure in a portion thereof.
• the protecting group is an alkyl-substituted silyl group
• R 14 represents an alkylene group having 1 to 30 carbon atoms which may have an aliphatic or aromatic substituent, or a conjugated diene polymer having 1 to 20 carbon atoms.
• R 12 and R 13 each independently represent at least one selected from the group consisting of an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 14 carbon atoms, an aralkyl group having 6 to 20 carbon atoms, and a protecting group; R 12 and R 13 may be bonded together to form a cyclic structure together with the adjacent nitrogen atom, in which case R 12 and R 13 represent an alkyl group having 5 to 12 carbon atoms, which may have an unsaturated bond or a branched structure in a portion thereof.
• the protecting group is an alkyl-substituted silyl group
• R 19 represents a hydrocarbon group having 1 to 30 carbon atoms which may have an aliphatic or aromatic substituent
• R 20 represents a hydrocarbon group having 1 to 12 carbon atoms which may have a substituted amino group
• n represents an integer from 1 to 10.
• R 15 and R 16 each independently represent at least one selected from the group consisting of an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 14 carbon atoms, an aryl group having 6 to 20 carbon atoms, and a protecting group; R 15 and R 16 may be bonded together to form a cyclic structure together with the adjacent nitrogen atom, in which case R 15 and R 16 represent an alkyl group having 5 to 12 carbon atoms, which may have a branched structure in part.
• the protecting group is an alkyl-substituted silyl group.
• R 17 represents a hydrocarbon group having 2 to 10 carbon atoms, which may have an unsaturated bond or a branched structure in a portion thereof.
• R 18 represents an alkyl group having 1 to 12 carbon atoms or a protecting group, which may have a branched structure in a portion thereof.
• the protecting group is an alkyl-substituted silyl group.
• examples of R 10 and R 11 include a methyl group, an ethyl group, a propyl group, a butyl group, an octyl group, a benzyl group, a cyclopropyl group, a cyclohexyl group, a 3-phenyl-1-propyl group, an isobutyl group, a decyl group, a heptyl group, and a phenyl group.
• R 10 and R 11 are not limited to these and include similar groups as long as they satisfy the above conditions.
• a butyl group and a hexyl group are preferred, and a butyl group is more preferred.
• Organolithium compounds having at least one nitrogen atom in the molecule represented by formula (1) include, but are not limited to, ethylpropylaminolithium, ethylbutylaminolithium, ethylbenzylaminolithium, dibutylaminolithium, dihexylaminolithium, etc., of which dibutylaminolithium and dihexylaminolithium are preferred, with dibutylaminolithium being more preferred.
• examples of the organolithium compound represented by the formula (1) include, but are not limited to, piperidinolithium, hexamethyleneiminolithium, lithium azacyclooctane, lithium-1,3,3-trimethyl-6-azabicyclo[3.2.1]octane, 1,2,3,6-tetrahydropyridinolithium, and 3,5-dimethylpiperidinolithium.
• the organolithium compound having at least one nitrogen atom in the molecule is not limited to these, and includes similar compounds thereof as long as the above conditions are satisfied.
• piperidinolithium, hexamethyleneiminolithium, lithium azacyclooctane, and lithium-1,3,3-trimethyl-6-azabicyclo[3.2.1]octane are preferred, piperidinolithium, hexamethyleneiminolithium, and 3,5-dimethylpiperidinolithium are more preferred, and piperidinolithium is even more preferred.
• R 14 represents an alkylene group having 1 to 30 carbon atoms which may have an aliphatic or aromatic substituent, or a conjugated diene polymer having 1 to 20 carbon atoms.
• the conjugated diene polymer preferably represents a polymer having a repeating unit of a conjugated diene compound having 4 to 12 carbon atoms.
• examples of the conjugated diene compound include 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.
• R 14 when R 14 represents an alkylene group having 1 to 30 carbon atoms, from the viewpoint of reactivity and interactivity with inorganic fillers such as carbon and silica, R 14 preferably represents an alkylene group having 2 to 20 carbon atoms, and more preferably represents an alkylene group having 3 to 16 carbon atoms.
• examples of the organolithium compound represented by formula (2) include, but are not limited to, (3-(dimethylamino)-propyl)lithium, (3-(diethylamino)-propyl)lithium, (3-(dipropylamino)-propyl)lithium, (3-(dibutylamino)-propyl)lithium, (3-(dipentylamino)-propyl)lithium, (3-(dihexylamino)-propyl)lithium, (3-(dioctylamino)-propyl)lithium, (3-(ethylhexylamino)-propyl)lithium, (3-(didecylamino)-propyl)lithium, (3-(ethylpropylamino-propyl)lithium, (3-(ethylbutylamino)-propyl)lithium, [0036
• the organolithium compound having at least one nitrogen atom in the molecule is not limited to these, and includes similar compounds as long as the above conditions are met. From the viewpoint of reactivity and interaction with inorganic fillers such as carbon and silica, (3-(dibutylamino)-propyl)lithium is more preferred.
• the organolithium compound represented by the formula (2) is not limited to the following, for example, (4-(dimethylamino)-2-butenyl)lithium, (4-(diethylamino)-2-butenyl)lithium, (4-(dibutylamino)-2-butenyl)lithium, (4-(dipropylamino)-2-butenyl)lithium, (4-(diheptylamino)-2-butenyl)lithium, (4-(dihexylamino)-2-butenyl)lithium, (4-(di (4-(di-2-ethylhexylamino)-2-butenyl)lithium, (4-(didecylamino)-2-butenyl)lithium, (4-(ethylpropylamino)-2-butenyl)lithium, (4-(ethylbutylamino
• the organolithium compound having at least one nitrogen atom in the molecule is not limited to these, and includes similar compounds thereof as long as the above conditions are satisfied. From the viewpoint of reactivity as an initiator and control of a chain transfer reaction described later, 4-(dimethylamino)-2-butenyl)lithium, (4-(diethylamino)-2-butenyl)lithium, and (4-(dibutylamino)-2-butenyl)lithium are preferred, and (4-(dibutylamino)-2-butenyl)lithium is more preferred.
• examples of the organolithium compound represented by the formula (2) include (3-(piperidinyl)propyl)lithium, (3-(hexamethyleneiminyl)propyl)lithium, (3-(heptamethyleneiminyl)propyl)lithium, (3-(octamethyleneiminyl)propyl)lithium, (3-(1,3,3-trimethyl-6-azabicyclo[3.2.1]octanyl)propyl)lithium, (3-(1,2,3,6-tetrahydropyridinyl)propyl)lithium, (2-(hexamethyleneiminyl)ethyl)lithium, (4-(hexamethyleneiminyl)butyl)lithium, (5-(hexamethyleneiminyl)pentyl)lithium, (6-(hexamethyleneiminyl)propyl)lithium, (7
• the organolithium compound having at least one nitrogen atom in the molecule is not limited to these, and includes similar compounds thereof as long as the above conditions are satisfied.
• inorganic fillers such as carbon and silica
• 3-(piperidinyl)propyl)lithium, (3-(hexamethinleniminyl)propyl)lithium, (3-(1,2,3,6-tetrahydropyridinyl)propyl)lithium, (4-(piperidinyl)-2-butenyl)lithium, and (4-(hexamethinleniminyl)-2-butenyl)lithium are preferred, and (3-(hexamethinleniminyl)propyl)lithium, (4-(piperidinyl)-2-butenyl)lithium, and (4-(hexamethinleniminyl)-2-butenyl)lithium are more preferred, and (4-(piperidin
• R 12 and R 13 are the same as R 12 and R 13 in formula (2).
• the organolithium compound having at least one nitrogen atom in the molecule represented by formula (3) may be a reaction product of an organomonolithium compound and an organic unsaturated compound having a substituted amino group.
• R20 is an organic group derived from an organic monolithium compound
• R19 is an alkylene compound derived from an organic unsaturated compound having a substituted amino group.
• R20 is a hydrocarbon group having a substituted amino group.
• organic unsaturated compound having a substituted amino group a known organic unsaturated compound having a substituted amino group that undergoes an addition reaction with a lithium-based initiator is used, and includes a vinyl aromatic compound having a substituted amino group and a conjugated diene compound having a substituted amino group.
• the organolithium compound having at least one nitrogen atom in the molecule represented by formula (3) is, but is not limited to, for example, 1-(4-N,N-dimethylaminophenyl)hexyllithium, 1-(4-N,N-dimethylaminophenyl)-1-phenylhexyllithium, 1-(4-N,N-dimethylaminomethylphenyl)hexyllithium, 1-(4-N,N-bistrimethylsilylaminophenyl)hexyllithium, 1-(4-N-trimethylsilyl-N-ethylaminophenyl)hexyllithium, 1-(4-N,N-bistrimethylsilylaminophenyl)-1-phenylhexyllithium, reaction product of 1 mole of butyllithium and 2 moles of 4-N,N-dimethylaminostyrene, reaction product of 1 mole of sec-butyllithium and 4 moles of
• the organolithium compound having at least one nitrogen atom in the molecule represented by the formula (4) includes a reaction product of an N-substituted orthotoluidine compound with an alkyllithium.
• the organolithium compound having at least one nitrogen atom in the molecule represented by formula (4) is not limited to the following, and examples thereof include N,N-dimethyl-o-toluidino lithium, N,N-dimethyl-m-toluidino lithium, N,N-dimethyl-p-toluidino lithium, N,N-diethyl-o-toluidino lithium, N,N-diethyl-m-toluidino lithium, N,N-diethyl-p-toluidino lithium, N,N-dipropyl-o-toluidino lithium, N,N-dipropyl-m-toluidino lithium, N,N-dipropyl-p-toluidino lithium, N,N-dibutyl-o-toluidin
• the organolithium compound having at least one nitrogen atom in the molecule is not limited to these, and includes similar compounds thereof as long as the above conditions are satisfied. From the viewpoint of polymerization activity, N,N-dimethyl-o-toluidino lithium is more preferable.
• Organolithium compounds having at least one nitrogen atom in the molecule represented by formula (4) include, but are not limited to, 2-(2-methylpiperidinyl)-1-ethyllithium (e.g., trade name "AI-250" manufactured by FMC Corporation).
• the organolithium compound is not limited to these, and includes similar compounds thereof as long as the above conditions are met.
• an organolithium compound having at least one nitrogen atom in the molecule or other organolithium compounds may be prepared in advance, and any known method can be used for this purpose.
• a step of copolymerizing at least a conjugated diene compound and a copolymerizable monomer having at least one nitrogen atom in the molecule in the presence of an organolithium compound may be carried out.
• the copolymerizable monomer having at least one nitrogen atom in the molecule a known organic unsaturated compound having a substituted amino group that copolymerizes with a conjugated diene compound by a lithium-based initiator is used, and includes a vinyl aromatic compound having a substituted amino group and a conjugated diene compound having a substituted amino group.
• the organolithium compound is preferably an organomonolithium compound, which may or may not have a substituted amino group in the molecule.
• an alkyllithium compound is preferred.
• a conjugated diene polymer having an alkyl group at the polymerization initiation terminal is obtained.
• the alkyllithium compound include, but are not limited to, n-butyllithium, sec-butyllithium, tert-butyllithium, n-hexyllithium, benzyllithium, phenyllithium, stilbenelithium, etc.
• n-butyllithium and sec-butyllithium are preferred from the viewpoints of industrial availability and ease of control of the polymerization reaction.
• the substituted amino group is an amino group in which the hydrogen atoms of the amino group are each independently substituted with at least one selected from the group consisting of an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 14 carbon atoms, an aralkyl group having 6 to 20 carbon atoms, and a protecting group, and the substituents may bond together to form a ring structure with the adjacent nitrogen atom, in which case the substituent represents an alkyl group having 5 to 12 carbon atoms, and may have an unsaturated bond or a branched structure in part.
• the protecting group is preferably an alkyl-substituted silyl group.
• the polymerization branching step is carried out in an inert solvent.
• inert solvents include, but are not limited to, hydrocarbon solvents such as saturated hydrocarbons and aromatic hydrocarbons.
• hydrocarbon solvents include, but are not limited to, aliphatic hydrocarbons such as butane, pentane, hexane, and heptane; alicyclic hydrocarbons such as cyclopentane, cyclohexane, methylcyclopentane, and methylcyclohexane; aromatic hydrocarbons such as benzene, toluene, and xylene; and hydrocarbons consisting of mixtures thereof.
• aliphatic hydrocarbons such as butane, pentane, hexane, and heptane
• alicyclic hydrocarbons such as cyclopentane, cyclohexane, methylcyclopentane, and methylcyclohexane
• aromatic hydrocarbons such as benzene, toluene, and xylene
• hydrocarbons consisting of mixtures thereof include, but are not limited to, aliphatic hydrocarbons such as butane, pentane
• the polymerization reaction in the polymerization branching step may be carried out using, for example, the following method as described in JP-A-59-140211. That is, a method may be used in which the polymerization reaction is first started using the entire amount of the vinyl aromatic compound and a portion of the conjugated diene compound, and then the remaining conjugated diene compound is intermittently added during the polymerization reaction.
• the polymerization temperature in the polymerization reaction in the polymerization branching step is not particularly limited, but is preferably a temperature at which living anionic polymerization proceeds. From the viewpoint of improving productivity, it is more preferably 0°C or higher, and even more preferably 0°C or higher and 120°C or lower. By having the polymerization temperature in the polymerization reaction within the above range, there is a tendency to be able to sufficiently increase the reactivity with the coupling modifier in the coupling step described below. From the same viewpoint, the polymerization temperature in the polymerization reaction is even more preferably 50°C or higher and 100°C or lower.
• a polar compound may be added.
• polar compounds When a polar compound is added, it tends to be possible to obtain a conjugated diene polymer in which a vinyl aromatic compound and a conjugated diene compound are randomly copolymerized in a single layer.
• polar compounds have an effective randomizing effect in the copolymerization of a conjugated diene compound and a vinyl aromatic compound, and therefore can be used as an agent for adjusting the distribution of the vinyl aromatic compound and the amount of styrene blocks.
• polar compounds can promote the polymerization reaction and can also be used as a vinylizing agent for controlling the microstructure of the conjugated diene polymer.
• the manufacturing method of this embodiment can increase the branching degree of the polymer by a branching agent described later, so that the branching degree can be controlled independently of the vinylation rate and randomization rate, which is advantageous in terms of structural design of the conjugated diene polymer.
• Polar compounds 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 tert-amylate; and phosphine compounds such as triphenylphosphine. These polar compounds may be used alone or in combination of two or more.
• ethers such as tetrahydrofuran, dieth
• the amount of polar compound added is not particularly limited, but can be adjusted according to the amount of polymerization active terminals, i.e., the amount of polymerization initiator added.
• the amount of polar compound added is, for example, preferably 0.010 mol or more and 1.0 mol or less, and more preferably 0.10 mol or more and 0.70 mol or less, relative to 1 mol of polymerization initiator. In the above range, the amount of polar compound added may be 0.60 mol or less or 0.50 mol or less, relative to 1 mol of polymerization initiator. Alternatively, it may be 0.15 mol or more or 0.20 mol or more, relative to 1 mol of polymerization initiator.
• the amount of polar compound added may be within a range that combines the above upper and lower limits in any way.
• a step of removing impurities may be included before the polymerization branching step.
• the above-mentioned monomer, polymerization initiator, and/or inert solvent contain allenes and acetylenes as impurities, it is preferable to include a step of removing impurities before the polymerization branching step.
• Such a step of removing impurities is not particularly limited, but for example, a step of treating with an organometallic compound is included.
• an organometallic compound is not particularly limited, but for example, an organolithium compound is included, and for example, an organolithium compound is not particularly limited, but for example, n-butyllithium is included.
• the branching reaction is initiated in the modified conjugated diene polymer by adding a branching agent described later. After the branching agent is added, the polymerization reaction in which the modified conjugated diene polymer grows and the branching reaction in which the modified conjugated diene polymer branches occur in competition with each other in the reaction system.
• the type and amount of branching agent as well as the timing of adding the branching agent, it is possible to control the weight average molecular weight, number average molecular weight, ratio thereof (Mw/Mn), and absolute molecular weight of the modified conjugated diene polymer obtained in the polymerization branching step, as well as the branching degree, number of branching points, and number of branches at the branching points of the conjugated diene polymer.
• the total amount of active ends of the conjugated diene polymer in the reaction system can be reduced compared to the amount of polymerization initiator added, and even if a small amount of polar compound is added, the reaction at the beginning of polymerization can be promoted and the activity of the polymerization active ends can be maintained.
• the conjugated diene polymer of this embodiment in which the amount of bound vinyl aromatic compound and the amount of vinyl bond are within the above-mentioned specified range, the coupling rate and/or modification rate of the polymerization end can be easily improved.
• the amount of polar compound added can be adjusted for the purpose of controlling the microstructure such as the amount of bound vinyl aromatic compounds and the amount of vinyl bonds.
• the amount of polar compound added that is usually used to set the amount of bound vinyl aromatic compounds and the amount of vinyl bonds to the above-mentioned predetermined range is insufficient from the viewpoint of maintaining the active terminal of the conjugated diene polymer in the reaction system when a branching agent is not added, and it is not easy to sufficiently maintain the activity of the polymerization active terminal.
• the randomization ability for the vinyl aromatic compounds and the conjugated diene compounds is not sufficiently high, and in the conjugated diene polymer of the present embodiment in which the amount of bound vinyl aromatic compounds and the amount of vinyl bonds are in the above-mentioned predetermined range, the polymerization terminal tends to be a vinyl aromatic compound. In such a state, it tends to be difficult to obtain a conjugated diene polymer with a high coupling rate or modification rate.
• a branching agent is used, so that even with an added amount of a polar compound in which it is usually not easy to sufficiently maintain the activity of the polymerization active terminal, the active terminal of the polymer can be sufficiently maintained, and a high coupling rate and modification rate can be achieved.
• the timing of adding the branching agent is not particularly limited, and can be appropriately selected depending on the application of the conjugated diene polymer to be produced.
• the timing of adding the branching agent is preferably a timing when the raw material conversion rate after the addition of the polymerization initiator is 20% or more, more preferably 40% or more, even more preferably 50% or more, even more preferably 65% or more, and even more preferably 75% or more.
• the timing of adding the branching agent is preferably a timing when the polymerization reaction is sufficiently stable.
• the branching agent is not particularly limited, but for example, a compound represented by the following formula (10) or formula (11) can be used.
• R 1 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, and may have a branched structure in part.
• R 2 and R 3 each independently represent an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, which may partially have a branched structure. When a plurality of R 1 to R 3 are present, they are each independent.
• X1 independently represents a halogen atom.
• m is an integer of 0 to 2
• n is an integer of 0 to 3
• 1 is an integer of 0 to 3.
• R 4 to R 7 each independently represent an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, which may partially have a branched structure. When a plurality of R 4 to R 7 are present, they are each independent.
• X 2 and X 3 each independently represent a halogen atom.
• m is an integer of 0 to 2
• n is an integer of 0 to 3
• 1 is an integer of 0 to 3.
• (m+n+l) represents 3.
• a represents an integer of 0 to 3
• b represents an integer of 0 to 2
• c represents an integer of 0 to 3.
• (a+b+c) represents 3.)
• Branching agents represented by the formula (10) include, but are not limited to, for example, trimethoxy(4-vinylphenyl)silane, triethoxy(4-vinylphenyl)silane, tripropoxy(4-vinylphenyl)silane, tributoxy(4-vinylphenyl)silane, triisopropoxy(4-vinylphenyl)silane, trimethoxy(3-vinylphenyl)silane, triethoxy(3-vinylphenyl)silane, tripropoxy(3-vinylphenyl)silane, tributoxy(3-vinylphenyl)silane, triisopropoxy(3-vinylphenyl)silane, trimethoxy(2-vinylphenyl)silane, (vinyl)silane, triethoxy(2-vinylphenyl)silane, tripropoxy(2-vinylphenyl
• examples of the branching agent represented by the formula (10) include trimethoxy(4-isopropenylphenyl)silane, triethoxy(4-isopropenylphenyl)silane, tripropoxy(4-isopropenylphenyl)silane, tributoxy(4-isopropenylphenyl)silane, triisopropoxy(4-isopropenylphenyl)silane, trimethoxy(3-isopropenylphenyl)silane, and triethoxy(3-isopropenylphenyl)silane.
• Branching agents represented by the formula (11) include, but are not limited to, 1,1-bis(4-trimethoxysilylphenyl)ethylene, 1,1-bis(4-triethoxysilylphenyl)ethylene, 1,1-bis(4-tripropoxysilylphenyl)ethylene, 1,1-bis(4-tripentoxysilylphenyl)ethylene, 1,1-bis(4-triisopropoxysilylphenyl)ethylene, 1,1-bis(3-trimethoxysilylphenyl)ethylene, 1,1-bis(3-triethoxysilylphenyl)ethylene, 1,1-bis(3-tripropoxysilylphenyl)ethylene, 1,1-bis(3-tripentoxysilylphenyl)ethylene, 1,1-bis(3-triisopropoxysilylphenyl)ethylene, 1,1-bis(2 -trimethoxysilylphenyl)ethylene, 1,1-bis(2-triethoxysilylphenyl)ethylene
• 1,1-bis(4-trimethoxysilylphenyl)ethylene, 1,1-bis(4-triethoxysilylphenyl)ethylene, 1,1-bis(4-tripropoxysilylphenyl)ethylene, 1,1-bis(4-tripentoxysilylphenyl)ethylene, and 1,1-bis(4-triisopropoxysilylphenyl)ethylene are preferred, with 1,1-bis(4-trimethoxysilylphenyl)ethylene being more preferred.
• the amount of such a branching agent to be added is not particularly limited and can be appropriately selected depending on the intended use of the conjugated diene polymer, but is preferably 0.020 mol or more and 0.50 mol or less, more preferably 0.025 mol or more and 0.40 mol or less, and even more preferably 0.030 mol or more and 0.25 mol or less, relative to 1 mol of the polymerization initiator.
• the amount of the branching agent added may be 0.040 mol or more or 0.045 mol or more per mol of the polymerization initiator, or 0.20 mol or less or 0.18 mol or less per mol of the polymerization initiator, in the above range.
• the amount of branching agent added may be within a range that is any combination of the upper and lower limits described above.
• the amount of branching agent added affects the degree of branching of the entire polymer, and as the amount added increases, the degree of branching of the entire polymer and the degree of branching at the extreme values increases.
• the reaction temperature may or may not be changed after the branching agent is added.
• the monomer of the conjugated diene polymer may be further added, and then the branching agent may be further added, and the addition of the branching agent and the monomer may be repeated.
• the monomer to be added is not particularly limited, but from the viewpoint of improving the modification rate in the coupling step, it is preferable to add the same monomer as that added initially as the monomer in the polymerization branching step.
• the amount of the added monomer may be 1.0% or more, 5.0% or more, 10.0% or more, 15.0% or more, or 20.0% or more of the total amount of monomers used for the conjugated diene polymer, and may be 50.0% or less, 40.0% or less, or 35.0% or less.
• the amount of the added monomer is within the above range, the molecular weight between the branching point generated by adding the branching agent and the branching point generated by adding the coupling modifier becomes long, so that the polymer tends to have a highly linear molecular structure.
• the entanglement of the molecular chains of the conjugated diene polymer increases when the polymer is vulcanized, and the vulcanized product tends to have excellent abrasion resistance, handling stability and breaking strength.
• conjugated diene polymer having a branched structure obtained by the above-mentioned polymerization and branching step it is preferable to react the conjugated diene polymer having a branched structure obtained by the above-mentioned polymerization and branching step with a coupling modifier to obtain a modified conjugated diene polymer.
• a coupling step the conjugated diene polymer having a branched structure obtained by the polymerization and branching step can be modified with a nitrogen atom-containing functional group having affinity or binding reactivity with a filler.
• a plurality of conjugated diene polymers can be coupled. Therefore, the production method having such a coupling step can more reliably and simply obtain the above-mentioned conjugated diene polymer of this embodiment.
• the coupling modifier is not particularly limited as long as it is a reactive compound having a nitrogen atom-containing functional group having affinity or bonding reactivity with the filler and capable of reacting with the active terminal of the conjugated diene polymer and having two or more functional groups.
• Such coupling modifiers include, for example, coupling modifiers that contain a nitrogen atom and further have a group that contains a nitrogen atom and a silicon atom.
• Coupling modifiers having a group containing a nitrogen atom include, but are not limited to, isocyanate compounds, isothiocyanate compounds, isocyanuric acid derivatives, nitrogen-containing carbonyl compounds, nitrogen-containing vinyl compounds, nitrogen-containing epoxy compounds, imine compounds, and nitrogen-containing alkoxysilane compounds.
• Examples of amine compounds that do not have active hydrogen include tertiary amine compounds.
• Isocyanate compounds 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.
• Isothiocyanate compounds include, but are not limited to, 2,4-tolylene diisothiocyanate, 2,6-tolylene diisothiocyanate, diphenylmethane diisothiocyanate, phenyl isothiocyanate, isophorone diisothiocyanate, hexamethylene diisothiocyanate, butyl isothiocyanate, 1,3,5-benzene triisothiocyanate, etc.
• Isocyanuric acid derivatives 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.
• Nitrogen atom-containing carbonyl compounds 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-2-piperid ...
• Examples include lysyl 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,N-methyl diethylcarbamate, N,N-diethylacetamide, N,N-dimethyl-N',N'-dimethylaminoacetamide, N,N-dimethylpicolinic acid amide, and N,N-dimethylisonicotinic acid amide.
• Nitrogen atom-containing vinyl compounds 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.
• nitrogen-containing epoxy compound examples include, but are not limited to, hydrocarbon compounds containing an epoxy group bonded to an amino group.
• the hydrocarbon compound may further have an epoxy group bonded to an ether group.
• nitrogen-containing epoxy compounds include, but are not limited to, compounds represented by the following formula (12):
• R is a divalent or higher organic group having at least one polar group selected from a divalent or higher hydrocarbon group, a polar group having oxygen such as ether, epoxy, or ketone, a polar group having sulfur such as thioether or thioketone, or a polar group having nitrogen such as a tertiary amino group or 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 24 and R 27 are hydrocarbon groups having 1 to 10 carbon atoms, and R 24 and R 27 may be the same or different.
• R 25 and R 28 are each a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and R 25 and R 28 may be the same or different.
• R 26 is a hydrocarbon group having 1 to 10 carbon atoms, or a structure represented by the following formula (13).
• R 24 , R 25 and R 26 may be bonded to each other to form a cyclic structure.
• R 26 when R 26 is a hydrocarbon group, it may be a cyclic structure bonded to R. In the case of the cyclic structure, the N bonded to R 26 and R may be directly bonded to each other.
• f is an integer of 1 or more
• g is 0 or an integer of 1 or more.
• R 29 and R 30 are defined similarly to R 24 and R 25 in the formula (12), and R 29 and R 30 may be the same or different.
• the nitrogen-containing epoxy compound is preferably a nitrogen-containing epoxy compound having one or more diglycidylamino groups and one or more glycidoxy groups in the molecule.
• nitrogen atom-containing epoxy compound examples 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-xylylenediamine, glycidyl-p-phenylenediamine, 4,4'-bis(diglycidylamino)
• Imine compounds include, but are not limited to, N-butylpropan-2-imine, N-butyl-4-methylpentan-2-imine, N,N'-(propane 1,3-diyl)bis(4-methylpentan-2-imine), N,N'-(hexane 1,6-diyl)bis(4-methylpentan-2-imine), tris[2-(propan-2-ylideneamino)ethyl]amine, tris[2-(propan-2-ylideneamino)propyl]amine, N,N'-(1,4-phenylene)bis(4-methylpentan-2-imine), 1,1'-(1,4-phenylene)bis(N-propylethane-1-imine), N,N'-(propane 1,3-diyl)bis(1-phenylmethanimine), N,N'-(hexane 1,6-diyl)bis(1-phenylme
• Nitrogen atom-containing alkoxysilane compounds include, but are not limited to, 3-dimethylaminopropyltrimethoxysilane, 3-dimethylaminopropylmethyldimethoxysilane, 3-diethylaminopropyltriethoxysilane, 3-morpholinopropyltrimethoxysilane, 3-piperidinopropyltriethoxysilane, 3-hexamethyleneiminopropylmethyldiethoxysilane, 3-(4-methyl-1-piperazino)propyltriethoxysilane, 3-(4-methyl-1-piperazino)propyltrimethoxysilane, 1-[3-(triethoxysilyl)-propyl]-propyl pyr]-3-methylhexahydropyrimidine, 3-(4-trimethylsilyl-1-piperazino)propyltriethoxysilane, 3-(3-triethylsilyl-1-imidazolid
• Preferred nitrogen atom-containing alkoxysilane compounds include, but are not limited to, 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 ("N,N,N',N'-tetrakis(3-trimethoxysilylpropyl)-1,3-propanediamine").
• examples of protected amine compounds in which active hydrogen is replaced with a protecting group include compounds having an unsaturated bond and a protected amine in the molecule.
• examples of such compounds include, but are not limited to, 4,4'-vinylidene bis[N,N-bis(trimethylsilyl)aniline], 4,4'-vinylidene bis[N,N-bis(triethylsilyl)aniline], 4,4'-vinylidene bis[N,N-bis(t-butyldimethylsilyl)aniline], 4,4'-vinylidene bis[N-methyl-N-(trimethylsilyl)aniline], 4,4'-vinylidene bis[N-ethyl-N-(trimethylsilyl)aniline], 4,4'-vinylidene bis[N-methyl-N-(triethylsilyl)aniline], Examples include 4,4'-vinylidenebis[N,N-bis(trimethylsilyl)aniline], 4,4
• 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)aminopropyltrimethoxysilane, N,N-bis(trimethylsilyl)aminopropylmethyldimethoxysilane, N,N-bis(trimethylsilyl)aminopropyltriethoxysilane, N,N-bis(trimethylsilyl)aminopropylmethyldiethoxysilane, N,N-bis(trimethylsilyl)aminoethyltrimethoxysilane, N,N-bis(trimethylsilyl)aminoethylmethyldiethoxysilane, N,N-bis(triethylsilyl)aminoethyl propylmethyldie
• N-ethylidene-3-methyl(dimethoxysilyl)-1-propanamine N-ethylidene-3-methyl(diethoxysilyl)-1-propanamine, N-(1-methylpropylidene)-3-(triethoxysilyl)-1-propanamine, N-(1-methylpropylidene)-3-(trimethoxysilyl)-1-propanamine, N-(1-methylpropylidene)-3-methyl(dimethoxysilyl)-1-propaneamine Amines, N-(1-methylpropylidene)-3-methyl(diethoxysilyl)-1-propanamine, N-benzylidene-3-methyl(dimethoxysilyl)propan-1-amine, N-benzylidene-3-methyl(diethoxysilyl)propan-1-amine, N-4-methylbenzylidene-3-(triethoxysilyl)propan-1-amine, N-4-methylbenzyliden
• the coupling step it is more preferable to use a combination of two or more types of nitrogen-containing alkoxysilane compounds represented by any one of the following formulas (14) to (18) as the coupling modifier.
• a coupling modifier having two or less alkoxysilyl groups and a coupling modifier having more than two alkoxysilyl groups can be used in combination.
• R 8 to R 10 are hydrocarbon groups having 1 to 20 carbon atoms which may have an unsaturated bond and may be the same or different.
• R 11 and R 12 are aliphatic hydrocarbon groups having 1 to 6 carbon atoms which may have an unsaturated bond and may be the same or different.
• R 13 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 have an unsaturated bond.
• d is an integer of 1 to 3.
• R 14 to R 16 are hydrocarbon groups having 1 to 20 carbon atoms, which may contain unsaturated bonds, and may be the same or different.
• R 17 and R 18 each represent 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 have an unsaturated bond.
• e represents an integer of 1 to 3.
• R 31 to R 34 each independently represent an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms
• R 35 represents an alkylene group having 1 to 10 carbon atoms
• R 36 represents an alkylene group having 1 to 20 carbon atoms.
• h represents an integer of 1 to 3
• i represents an integer of 1 or 2
• (h+i) represents an integer of 4 or greater.
• R 37 to R 42 each independently represent an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms
• R 43 to R 45 each independently represent an alkylene group having 1 to 20 carbon atoms.
• m, n, and l each independently represent an integer of 1 to 3, and (m+n+l) represents an integer of 4 or greater.
• R 46 to R 48 each independently represent a single bond or an alkylene group having 1 to 20 carbon atoms
• R 49 to R 52 each independently represent an alkyl group having 1 to 20 carbon atoms
• R 53 and R 56 each independently represent an alkylene group having 1 to 20 carbon atoms
• R 54 represents an alkylene group or an alkoxy group having 1 to 20 carbon atoms
• R 55 represents an alkyl group or a trialkylsilyl group having 1 to 20 carbon atoms.
• o represents an integer of 1 to 3
• p represents 1 or 2.
• 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 oxygen atoms, nitrogen atoms, silicon atoms, sulfur atoms, and phosphorus atoms and having no active hydrogen atoms.
• the coupling modifier represented by the formula (14) is not limited to the following, but examples thereof include 1-methyl-4-(3-(trimethoxysilyl)propyl)piperazine, 1-methyl-4-(3-(triethoxysilyl)propyl)piperazine, 1-ethyl-4-(3-(trimethoxysilyl)propyl)piperazine, 1-ethyl-4-(3-(triethoxysilyl)propyl)piperazine, 1-propyl-4-(3-(trimethoxysilyl)propyl)piperazine, 1-propyl-4-(3-(triethoxysilyl)propyl)piperazine, 1-butyl-4-(3-(trimethoxysilyl)propyl)piperazine, 1-butyl-4-(3-(triethoxysilyl)propyl)piperazine, 1-trimethylsilyl -4-(3-(trimethoxysilyl)propyl)piperaz
• d in formula (16) is 3 are preferred.
• 1-methyl-4-(3-(trimethoxysilyl)propyl)piperazine and 1-methyl-4-(3-(triethoxysilyl)propyl)piperazine are preferred.
• reaction temperature, reaction time, etc., when reacting the coupling modifier having a nitrogen atom-containing group represented by formula (14) with the polymerization active terminal are not particularly limited, but it is preferable to react at 0°C or higher and 120°C or lower for 30 seconds or more.
• the amount of the coupling modifier represented by the formula (14) added is preferably in a range in which the total number of moles of alkoxy groups (OR 8 ) bonded to silyl groups in the compound represented by the formula (14) is 0.2 to 2.5 times the number of moles of the polymerization initiator added, more preferably 0.5 to 2.0 times, and even more preferably 1.0 to 2.0 times. From the viewpoint of setting the modification rate and molecular weight of the obtained conjugated diene polymer in a more preferable range, it is preferably 0.2 times or more. Moreover, from the viewpoint of suppressing a decrease in processability due to an excessive increase in branching degree, it is preferably 2.5 times or less.
• the amount of the polymerization initiator and the coupling modifier represented by formula (14) added may be adjusted so that the number of moles of the polymerization initiator is preferably 1.5 times or more, more preferably 1.7 times or more, the number of moles of the coupling modifier represented by formula (14).
• Coupling modifiers represented by the formula (15) include, but are not limited to, N-(1,3-dimethylbutylidene)-3-(triethoxysilyl)-1-propanamine, N-(1,3-dimethylbutylidene)-3-(trimethoxysilyl)-1-propanamine, N-(1,3-dimethylbutylidene)-3-methyl(dimethoxysilyl)-1-propanamine, N-(1,3-dimethylbutylidene)-3-methyl(dimethoxysilyl)-1-propanamine, N-(1,3-dimethyl butylidene)-3-methyl(diethoxysilyl)-1-propanamine, N-(1-methylethylidene)-3-(triethoxysilyl)-1-propanamine, N-(1-methylethylidene)-3-(trimethoxysilyl)-1-propanamine, N-(1-methylethylidene)
• reaction temperature, reaction time, etc., when reacting the coupling modifier having a nitrogen atom-containing group represented by formula (15) with the polymerization active terminal are not particularly limited, but it is preferable to react at 0°C or higher and 120°C or lower for 30 seconds or longer.
• the amount of the coupling modifier represented by the formula (15) added is preferably in a range in which the total number of moles of alkoxy groups (OR 14 ) bonded to silyl groups in the compound represented by the formula (15) is 0.2 to 2.5 times the number of moles of the polymerization initiator added, more preferably 0.5 to 2.0 times, and even more preferably 1.0 to 2.0 times. From the viewpoint of setting the modification rate and molecular weight of the obtained conjugated diene polymer in a more preferable range, it is preferably 0.2 times or more. Moreover, from the viewpoint of suppressing a decrease in processability due to an excessive increase in branching degree, it is preferably 2.5 times or less.
• the amount of the polymerization initiator and the coupling modifier represented by formula (15) added may be adjusted so that the number of moles of the polymerization initiator is preferably 1.5 times or more, more preferably 1.7 times or more, the number of moles of the coupling modifier represented by formula (15).
• Coupling modifiers having a group containing a nitrogen atom represented by the formula (16) include, but are not limited to, 2,2-dimethoxy-1-(3-trimethoxysilylpropyl)-1-aza-2-silacyclopentane, 2,2-diethoxy-1-(3-triethoxysilylpropyl)-1-aza-2-silacyclopentane, 2,2-dimethoxy-1-(4-trimethoxysilylbutyl)-1-aza-2-silacyclohexane, 2,2-dimethoxy-1-(5-trimethoxysilylpentyl)-1-aza-2-silacycloheptane, 2,2-dimethoxy-1-(3-dimethoxymethylsilylpropyl)- Examples include 1-aza-2-silacyclopentane, 2,2-diethoxy-1-(3-diethoxyethylsilylpropyl)-1-aza-2-silacyclopentane, 2-
• reaction temperature and reaction time are not particularly limited, but are preferably from 0°C to 120°C, and the reaction time is preferably 30 seconds or longer.
• the amount of the coupling modifier represented by formula (16) 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 (16) is 0.2 to 2.5 times the number of moles of the polymerization initiator added, more preferably 0.5 to 2.0 times, and even more preferably 1.0 to 2.0 times. From the viewpoint of setting the modification rate, molecular weight, and branched structure of the resulting conjugated diene polymer in a more preferable range, it is preferably 0.2 times or more. Also, from the viewpoint of preventing a decrease in processability due to an excessive increase in the branching degree, it is preferably 2.5 times or less.
• the amount of the polymerization initiator and the coupling modifier represented by formula (16) added may be adjusted so that the number of moles of the polymerization initiator is preferably 3.0 times or more, more preferably 4.0 times or more, relative to the number of moles of the coupling modifier represented by formula (16).
• Modifiers having a nitrogen atom-containing group represented by formula (17) 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, tris(4-trimethoxysilylbutyl)amine, etc.
• n, m, and l all represent 3.
• Preferred examples include tris(3-trimethoxysilylpropyl)amine and tris(3-triethoxysilylpropyl)amine.
• reaction temperature, reaction time, etc., when reacting the modifying agent having a nitrogen atom-containing group represented by formula (17) with the polymerization active terminal are not particularly limited, but it is preferable to react at 0°C or higher and 120°C or lower for 30 seconds or more.
• the total number of moles of alkoxy groups bonded to silyl groups in the coupling modifier represented by formula (17) is preferably in the range of 0.2 to 2.0 times the number of moles of lithium constituting the above-mentioned polymerization initiator, more preferably in the range of 0.5 to 2.0 times, and even more preferably in the range of 0.6 to 1.6 times.
• the number of moles of the polymerization initiator is preferably 4.0 times or more, more preferably 5.0 times or more, relative to the number of moles of the modifier.
• A is preferably represented by any one of the following general formulas (i) to (iv).
• B 1 represents a single bond or a hydrocarbon group having 1 to 20 carbon atoms, and t represents an integer of 1 to 10. When a plurality of B 1 are present, each B 1 is independent.
• B2 represents a single bond or a hydrocarbon group having 1 to 20 carbon atoms
• B3 represents an alkyl group having 1 to 20 carbon atoms
• t represents an integer of 1 to 10.
• B 4 represents a single bond or a hydrocarbon group having 1 to 20 carbon atoms, and t represents an integer of 1 to 10. When a plurality of B 4s are present, each B 4 is independent.
• B 5 represents a single bond or a hydrocarbon group having 1 to 20 carbon atoms, and t represents an integer of 1 to 10. When a plurality of B 5s are present, each B 5 is independent.
• examples of coupling modifiers having a group containing a nitrogen atom when A is represented by the formula (i) 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 -dieth
• examples of coupling modifiers having a nitrogen atom-containing group when A is represented by the formula (ii) 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, tris(3-triethoxysilylpropyl)-methyl-1,3-propanediamine, bis(2-triethoxysilylpropyl)-[3-(2, 2-diethoxy-1-aza-2-silacyclopentane)propyl]-methyl-1,3-propanediamine,
• examples of coupling modifiers having a nitrogen atom-containing group when A is represented by the formula (iii) 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, -silacyclopentane)propyl]-[3-(1-methoxy-2-trimethylsilyl-1-sila-2-azacyclopentane)propyl]silane, bis(3-trimethoxysilylpropyl)-bis[3-(2,2-dimethoxy-1-
• examples of the modifying agent having a nitrogen atom-containing group 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, 3-tris[2-(2,2-dimethoxy-1-aza-2-silacyclopentane)ethoxy]silyl-1-trimethoxysilylpropane, etc.
• A is preferably represented by formula (i) or formula (ii), and s is 0.
• Coupling modifiers having such a nitrogen atom-containing group tend to be easily available, and also tend to provide better abrasion resistance and low hysteresis loss performance when the conjugated diene polymer is vulcanized.
• Examples of coupling modifiers having such a nitrogen atom-containing group include, but are not limited to, bis(3-trimethoxysilylpropyl)-[3-(2,2-dimethoxy-1-aza-2-silacyclopentane)propyl]amine, tris(3-trimethoxysilylpropyl)amine, tris(3-triethoxysilylpropyl)amine, tris(3-trimethoxysilylpropyl)-[3-(2,2-dimethoxy-1-aza-2-silacyclopentane)propyl]-1,3-propanediamine, tetrakis[3-(2,2- dimethoxy-1-aza-2-silacyclopentane)propyl]
• A is more preferably represented by formula (i) or formula (ii), s is 0, and in formula (i) or formula (ii), t is an integer from 2 to 10.
• Examples of coupling modifiers having a group containing a nitrogen atom include, but are not limited to, tetrakis[3-(2,2-dimethoxy-1-aza-2-silacyclopentane)propyl]-1,3-propanediamine, tetrakis(3-trimethoxysilylpropyl)-1,3-propanediamine, tetrakis(3-trimethoxysilylpropyl)-1,3-bisaminomethylcyclohexane, N 1 -(3-(bis(3-(trimethoxysilyl)propyl)amino)propyl)-N 1 -methyl-N 3 -(3-(methyl(3-(trimethoxysilyl)propyl)amino)propyl)-N 3 -(3-(trimethoxysilyl)propyl)-1,3-propanediamine, and the like.
• the amount of the compound represented by formula (18) added as a coupling modifier having a nitrogen atom-containing group can be adjusted so that the moles of the conjugated diene polymer to the moles of the coupling modifier react in a desired stoichiometric ratio, which tends to achieve the desired highly branched star structure.
• the specific number of moles of the polymerization initiator is preferably 5.0 times or more, more preferably 6.0 times or more, relative to the number of moles of the coupling modifier.
• the number of functional groups of the coupling modifier ((o-1) x q + p x r + s) is preferably an integer from 5 to 10, and more preferably an integer from 6 to 10.
• 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 the step of adding a coupling modifier and/or before the step of adding a coupling modifier to cause a condensation reaction.
• the method for producing a conjugated diene polymer of this embodiment may further include a modification step using a modifier other than the coupling modifier described above.
• two types of coupling modifiers may be added, or three or more types of coupling modifiers may be added.
• two types of coupling modifiers it is preferable to use a combination of coupling modifiers having different numbers of functional groups.
• three or more types of coupling modifiers it is preferable to include a combination of coupling modifiers having different numbers of functional groups.
• a coupling modifier In the step of adding a coupling modifier, it is preferable to add two types of coupling modifiers having different numbers of functional groups.
• An example of a combination of two types of coupling modifiers having different numbers of functional groups is a combination of a coupling modifier having two or less functional groups and a coupling modifier having three or more functional groups. It is preferable that multiple types of coupling modifiers are added simultaneously, and they may or may not be mixed in advance.
• the method for producing a conjugated diene polymer of this embodiment may include a hydrogenation step for hydrogenating the conjugated diene portion.
• the method for hydrogenating the conjugated diene portion is not particularly limited, and any known method can be used.
• a preferred hydrogenation step is a method in which gaseous hydrogen is blown into a polymer solution in the presence of a catalyst to hydrogenate the conjugated diene portion.
• the catalyst used is not particularly limited, but examples thereof include heterogeneous catalysts such as a catalyst in which a precious metal is supported on a porous inorganic substance; and homogeneous catalysts such as a catalyst in which a salt of nickel, cobalt, or the like is solubilized and reacted with an organoaluminum or the like, and a catalyst using a metallocene such as titanocene.
• titanocene catalysts are preferred from the viewpoint of being able to select milder hydrogenation conditions.
• a method for hydrogenating aromatic groups a method using a supported noble metal catalyst can be mentioned.
• Such hydrogenation catalysts are not particularly limited, but examples include (1) supported heterogeneous hydrogenation catalysts in which metals such as Ni, Pt, Pd, or Ru are supported on carbon, silica, alumina, diatomaceous earth, or the like, (2) so-called Ziegler-type hydrogenation catalysts that use transition metal salts such as organic acid salts or acetylacetone salts of Ni, Co, Fe, or Cr, etc., and reducing agents such as organoaluminum, and (3) so-called organometallic complexes such as organometallic compounds of Ti, Ru, Rh, or Zr, etc.
• hydrogenation catalysts include, but are not limited to, known hydrogenation catalysts described in, for example, JP-B-42-8704, JP-B-43-6636, JP-B-63-4841, JP-B-1-37970, JP-B-1-53851, JP-B-2-9041, and JP-A-8-109219.
• a preferred hydrogenation catalyst is a reaction mixture of a titanocene compound and a reducing organometallic compound.
• a deactivator and/or a neutralizer, etc. may be added to the polymer solution as necessary.
• quenching agents include, but are not limited to, water and alcohols such as methanol, ethanol, and isopropanol.
• Neutralizing agents include, but are not limited to, carboxylic acids such as stearic acid, oleic acid, and versatic acid (a mixture of highly branched carboxylic acids with 9 to 11 carbon atoms and mainly with 10 carbon atoms), aqueous solutions of inorganic acids, and carbon dioxide gas.
• carboxylic acids such as stearic acid, oleic acid, and versatic acid (a mixture of highly branched carboxylic acids with 9 to 11 carbon atoms and mainly with 10 carbon atoms), aqueous solutions of inorganic acids, and carbon dioxide gas.
• the method for producing a conjugated diene polymer of the present embodiment may include a step of obtaining the obtained conjugated diene polymer from a polymer solution.
• a known method can be used, and for example, the following method can be used. That is, examples of the method include a method in which the solvent is separated by steam stripping or the like, and the polymer is then filtered, and then dehydrated and dried to obtain a polymer; a method in which the polymer is concentrated in a flashing tank, and then devolatilized using a vent extruder or the like to obtain a polymer; and a method in which the polymer is directly devolatilized using a drum dryer or the like to obtain a polymer.
• the rubber composition of the present embodiment contains a rubber component containing the conjugated diene-based polymer of the present embodiment described above.
• the conjugated diene-based polymer of the present embodiment is blended into a tire, the oil contained in the veil molded body is inevitably contained in the tire. However, if the amount of oil extension is reduced, the oil contained in the tire is also reduced, which has the advantage of increasing the degree of freedom in the composition in tire design.
• the conjugated diene polymer and its sheet- or block-shaped molded product (also called a veil) of this embodiment may contain a softener component, which will be described later.
• the molded product (veil) preferably contains 2 parts by mass or less of a rubber softener relative to 100 parts by mass of the conjugated diene polymer, more preferably 1.5 parts by mass or less, even more preferably 1 part by mass or less, even more preferably less than 1 part by mass, and most preferably no softener is added.
• Rubber softeners are not particularly limited, but examples include extender oils, liquid rubber, and resins.
• the conjugated diene-based polymer and its sheet-like or block-like molded product are provided without the addition of a rubber softener, from the viewpoint of improving the degree of freedom in compounding design when producing a rubber composition using the molded product.
• a rubber softener is added to a sheet-like or block-like molded body of a conjugated diene polymer
• the rubber composition produced by compounding the molded body also contains the rubber material softener, which puts pressure on the total amount of rubber softeners in the entire rubber composition and limits the degree of freedom in the type and amount of rubber softeners that need to be compounded when producing the rubber composition.
• extender oil added to the conjugated diene polymer of this embodiment and its sheet-like or block-like molded product, it becomes possible to compound more resins such as extender oil when producing a rubber composition using these. This is preferable from the viewpoint of further improving the breaking strength of the rubber composition and its vulcanizate.
• the rubber composition using the conjugated diene polymer of this embodiment and the sheet- or block-shaped molded product thereof may further contain a rubber stabilizer from the viewpoint of suppressing gel formation and improving stability during processing.
• the rubber stabilizer is not limited to the following and any known stabilizer can be used, but examples include antioxidants such as 2,6-di-tert-butyl-4-hydroxytoluene (hereinafter also referred to as "BHT"), n-octadecyl-3-(4'-hydroxy-3',5'-di-tert-butylphenol) propionate, and 2-methyl-4,6-bis[(octylthio)methyl]phenol.
• antioxidants such as 2,6-di-tert-butyl-4-hydroxytoluene (hereinafter also referred to as "BHT"), n-octadecyl-3-(4'-hydroxy-3',5'-di-tert-butylphenol) propionate, and 2-methyl-4,6-bis[(octylthio)methyl]phenol.
• BHT 2,6-di-tert-butyl-4-hydroxytoluene
• the veil of the present embodiment contains 100 parts by mass of the modified conjugated diene polymer of the present embodiment and 2 parts by mass or less of a softener component.
• the veil of the present embodiment may also contain 100 parts by mass of the modified conjugated diene polymer of the present embodiment and less than 1 part by mass of a softener component.
• the rubber composition of the present embodiment includes 100 parts by mass of a rubber component and 5.0 parts by mass or more and 150 parts by mass or less of a filler, and the rubber component includes 10 parts by mass or more of the modified conjugated diene-based polymer of the present embodiment or the veil of the present embodiment per 100 parts by mass of the total amount of the rubber component.
• the rubber composition of the present embodiment comprises 100 parts by mass of a rubber component,
• the composition contains 5.0 parts by mass or more and 150 parts by mass or less of a filler.
• 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.
• 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 particularly 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 constituent unit are preferred, and solid particles containing SiO2 or Si3Al as a main component of the constituent 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.
• 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.
• Examples of silica include, but are not limited to, 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 conjugated diene polymer further improves the dispersibility of silica.
• the rubber composition obtained 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 5.0 parts by mass or more and 150 parts by mass or less, preferably 20 parts by mass or more and 100 parts by mass or less, and 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 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, from the viewpoint of reliably imparting the performance required for applications such as tires, such as dry grip performance and conductivity. From the same viewpoint, the rubber composition preferably contains 3.0 parts by mass or more and 100 parts by mass or less of carbon black, and 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.
• 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, bis-[2-(triethoxysilyl)-ethyl]-tetrasulfide, etc.
• 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 this embodiment may contain a rubber-like polymer (hereinafter simply referred to as a "rubber-like polymer”) other than the conjugated diene polymer of this embodiment as a rubber component.
• a rubber-like polymer hereinafter simply referred to as a "rubber-like polymer”
• the conjugated diene polymer of this embodiment and the rubber-like polymer are collectively referred to as the "rubber component.”
• 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, natural rubber, etc.
• Rubber-like polymers include, but are not limited to, styrene-based elastomers such as butadiene rubber and its hydrogenated products, isoprene rubber and its hydrogenated products, styrene-butadiene rubber and its hydrogenated products, styrene-butadiene block copolymers and their hydrogenated products, and styrene-isoprene block copolymers and their hydrogenated products, as well as acrylonitrile-butadiene rubber and its hydrogenated products.
• styrene-based elastomers such as butadiene rubber and its hydrogenated products, isoprene rubber and its hydrogenated products, styrene-butadiene rubber and its hydrogenated products, styrene-butadiene block copolymers and their hydrogenated products, and styrene-isoprene block copolymers and their hydrogenated products, 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, polysulfide rubber, etc.
• 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
• Natural rubber includes, but is not limited to, smoked sheets such as RSS3-5, 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 90/10 or less, and even more preferably 30/70 or more and 80/20 or less.
• the rubber component contains the conjugated diene polymer of the present 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 proportion of the conjugated diene polymer contained in the rubber component is within the above range, the vulcanizate of the rubber composition tends to be even more excellent in abrasion resistance and low hysteresis loss.
• the rubber composition of the present embodiment contains a softener component (for example, a rubber softener) in addition to the rubber component, from the viewpoint of further improving the processability.
• the softener component is not particularly limited, but examples thereof include liquid rubber, resin, and extender oil.
• the liquid rubber is not particularly limited, but examples thereof include liquid polybutadiene and liquid styrene-butadiene rubber.
• the resin examples include, but are not limited to, aromatic petroleum resins, coumarone-indene resins, terpene resins, rosin derivatives (including paulownia oil resins), tall oil, tall oil derivatives, 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, hydrocarbon resins, hydrogenated paulownia oil resins, hydrogenated oil resins, esters of hydrogenated oil resins and monofunctional or polyfunctional alcohols, etc.
• the breaking strength of the vulcanizate of the conjugated diene polymer composition tends to be further improved. From the viewpoint of further improving the breaking strength of the vulcanizate, it is preferable to add a resin as a softener component to the rubber composition of the present embodiment in addition to the rubber component.
• a softener component may be added in addition to the rubber component, but mineral oil or a liquid or low molecular weight synthetic softener is preferred.
• extender oils include aromatic oils, naphthenic oils, and paraffin oils.
• aromatic substitute oils having a polycyclic aromatic (PCA) content of 3% by mass or less according to the IP346 method are preferred from the viewpoint of environmental safety, prevention of oil bleeding, and improvement of wet grip performance.
• aromatic substitute oils include, but are not limited to, TDAE (Treated Distillate Aromatic Extracts), MES (Mild Extraction Solvate), and RAE (Residual Aromatic Extracts) shown in Kautschuk Kunststoffe 52(12)799(1999).
• Mineral oil-based rubber softeners are used to soften rubber, increase its volume, and improve its workability. They are mixtures of aromatic rings, naphthenic rings, and paraffin chains. Among them, those in which the number of carbons belonging to paraffin chains is 50% or more of the total number of carbons are called paraffinic, those in which the number of carbons belonging to naphthenic rings is 30% to 45% of the total number of carbons are called naphthenic, and those in which the number of carbons belonging to aromatic carbons is more than 30% of the total number of carbons are called aromatic.
• the rubber composition of this embodiment preferably contains a rubber softener with a moderate aromatic content. By containing such a rubber softener, compatibility with conjugated diene polymers is further improved.
• the content of the softener component in the rubber composition of this embodiment is represented by the total amount of the softener component added in advance to the conjugated diene polymer of this embodiment and the above-mentioned rubber-like polymer, and the softener component added when forming the rubber composition.
• the content of the softener component 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 content of the rubber softener be 100 parts by mass or less per 100 parts by mass of the rubber component, bleeding out can be suppressed and stickiness of the rubber composition surface can be further suppressed.
• the method for mixing the conjugated diene polymer of this embodiment, a rubber-like polymer other than the conjugated diene polymer of this embodiment, a filler, and if necessary, a silane coupling agent and a rubber softener, etc. is not particularly limited.
• examples include a melt-kneading method using 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 solvent is heated and removed after each component is dissolved and mixed.
• melt-kneading method using a roll, a Banbury mixer, a kneader, or an extruder is preferred from the viewpoints of productivity and good kneading properties.
• the rubber component, the filler, the silane coupling agent, and the additives may be kneaded at once, or may be mixed in several batches.
• the rubber composition of this embodiment may be vulcanized with a vulcanizing agent to form a vulcanizate.
• vulcanizing agents include, but are not limited to, 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 this embodiment may contain various additives such as softeners and fillers other than those described above, heat stabilizers, antistatic agents, weather stabilizers, antioxidants, colorants, and lubricants, within the scope of not impairing the effects of this embodiment.
• softener a known softener can be used.
• filler there is no particular limitation, but examples include calcium carbonate, magnesium carbonate, aluminum sulfate, and barium sulfate.
• heat stabilizer, antistatic agent, weather stabilizer, antioxidant, colorant, and lubricant known materials can be used.
• the tire of the present embodiment contains the rubber composition of the present embodiment described above.
• Examples of the tire according to the present embodiment include, but are not limited to, various types of tires such as fuel-efficient tires, all-season tires, high-performance tires, and studless tires.
• the rubber composition according to the present embodiment can be suitably used in each part of the tire such as the tread, carcass, sidewall, and bead portion.
• the eluent used was a 5 mmol/L triethylamine-THF (tetrahydrofuran) solution.
• 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 measurement results were taken as the average molecular weight of each sample.
• the eluent used was THF containing 5 mmol/L triethylamine.
• the columns used were "TSKgel G4000HXL", “TSKgel G5000HXL”, and "TSKgel G6000HXL” manufactured by Tosoh Corporation.
• the modification ratio of the modified conjugated diene polymer was measured by a column adsorption GPC method as follows.
• the column adsorption GPC method is a method for determining the modification rate of a modified polymer by utilizing the property that the modified basic polymer component in a modified conjugated diene polymer is easily adsorbed in a GPC column filled with a silica-based gel.
• the modified conjugated diene polymer was used as a sample, and a sample solution containing the sample and low molecular weight internal standard polystyrene was measured using a polystyrene column. The same sample solution was also measured using a silica column.
• the amount of the modified conjugated diene polymer adsorbed on the silica column was measured by calculating the difference between the chromatogram obtained by the measurement using the polystyrene column and the chromatogram obtained by the measurement using the silica column, and the modification rate was calculated.
• sample solution was prepared by dissolving 10 mg of a sample and 5 mg of standard polystyrene in 10 mL of THF.
• the modification rate of the modified conjugated diene polymer was measured under the following measurement conditions.
• GPC measurements were carried out using a Tosoh Corporation product name "HLC-8320GPC” and an RI detector (Tosoh Corporation product name "HLC8020”).
• HLC-8320GPC Tosoh Corporation product name "HLC8020”
• RI detector Tosoh Corporation product name "HLC8020”
• a 5 mmol/L triethylamine-THF solution was used as the eluent, and 10 ⁇ L of the sample solution was injected into the GPC apparatus to obtain a chromatogram under 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.
• the modified conjugated diene polymer was used as a sample, and 100 mg of the sample was dissolved in 100 mL of chloroform to prepare a measurement sample. Each sample was measured using a spectrophotometer (manufactured by Shimadzu Corporation under the trade name "UV-2450") to obtain an absorption spectrum. The amount of bound styrene (mass%) relative to 100 mass% of the modified conjugated diene polymer was calculated from the amount of absorbance of ultraviolet light (at around 254 nm) derived from the phenyl group of styrene.
• the content of the antioxidant in the modified conjugated diene polymer was measured by HPLC analysis as follows.
• THF tetrahydrofuran
• Nitrogen atom content (mass ppm)
• the modified conjugated diene polymer was used as a sample and the measurement was carried out in accordance with JIS-2609: Crude petroleum and petroleum products -- Nitrogen content test method, chemiluminescence method.
• the measuring device used was a total nitrogen trace analyzer ("TN-2100H” manufactured by Mitsubishi Chemical Analytech Co., Ltd.).
• the measurement method was as follows: a sample was thermally decomposed in a flow of argon gas, and then the sample was burned and oxidized with oxygen gas to produce nitric oxide, which was then subjected to an oxidation reaction with ozone gas under dehydrating conditions. The emission intensity at 590 to 2500 nm detected was measured, and the nitrogen content was calculated from the area value of the emission intensity.
• Example 1 Modified conjugated diene polymer (A1) 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 a stirrer and a jacket for temperature control, were connected together as polymerization branching reactors. 1,3-butadiene, styrene, and n-hexane, from which moisture had been removed in advance, were continuously fed to the bottom of the first reactor while being mixed at rates of 18.5 g/min, 6.2 g/min, and 117.4 g/min, respectively.
• n-butyllithium for inactivating remaining impurities was continuously added at a rate of 0.096 mmol/min while being mixed with a static mixer immediately before the mixed solution entered the first reactor.
• a mixed solution of piperidinolithium also called “1-lithiopiperidine”; abbreviated as "a-1" in the table
• n-butyllithium as a pre-prepared lithium amide as a polymerization initiator
• the conjugated diene polymer solution produced by the polymerization reaction in the first reactor was continuously withdrawn from the top of the first reactor and continuously fed to the bottom of the second reactor.
• trimethoxy(4-vinylphenyl)silane also referred to as "c-1"
• c-1 trimethoxy(4-vinylphenyl)silane
• a small amount of the conjugated diene polymer solution was withdrawn from the outlet of the second reactor, and an antioxidant (BHT) was added so that the amount of the antioxidant (BHT) was 0.2 g per 100 g of the conjugated diene polymer, and then the solvent was removed.
• the obtained conjugated diene polymer was subjected to measurement of various molecular weights by GPC measurement, Mooney viscosity at 110° C., Mooney relaxation rate, and the like.
• the physical properties are shown in Tables 1 to 3 (Physical Properties 1-1, 1-2, 1-3, Physical Properties 2, Physical Properties 3).
• the conjugated diene polymer solution flowing out from the top of the second reactor was supplied to a static mixer. Furthermore, tetrakis(3-trimethoxysilylpropyl)-1,3-propanediamine (also referred to as "b-1") was continuously added as a coupling modifier at a rate of 0.031 mmol/min to the conjugated diene polymer solution flowing continuously through the static mixer, thereby coupling the conjugated diene polymer. At this time, it took 4.8 minutes for the coupling modifier to be added to the polymer solution flowing out from the outlet of the second reactor, and the temperature of the polymer solution when the coupling modifier was added was 68°C. In addition, the difference between the temperature of the polymer solution at the outlet of the second reactor and the temperature of the polymer solution when the coupling modifier was added was 2°C.
• Example 2 Modified conjugated diene polymer (A2) A modified conjugated diene polymer (A2) was obtained in the same manner as in Example 1, except that b-1 as a coupling modifier was supplied at 0.044 mmol/min. The physical properties of the modified conjugated diene polymer (A2) are shown in Table 1.
• Example 3 Modified conjugated diene polymer (A3) A modified conjugated diene polymer (A3) was obtained in the same manner as in Example 1, except that b-1 as a coupling modifier was supplied at 0.054 mmol/min. The physical properties of the modified conjugated diene polymer (A3) are shown in Table 1.
• Example 4 Modified conjugated diene polymer (A4) A modified conjugated diene polymer (A4) was obtained in the same manner as in Example 1, except that b-1 as a coupling modifier was supplied at 0.062 mmol/min. The physical properties of the modified conjugated diene polymer (A4) are shown in Table 1.
• Example 5 Modified conjugated diene polymer (A5) A modified conjugated diene polymer (A5) was obtained in the same manner as in Example 1, except that b-1 as a coupling modifier was supplied at 0.070 mmol/min. The physical properties of the modified conjugated diene polymer (A5) are shown in Table 1.
• Example 6 Modified conjugated diene polymer (A6) A modified conjugated diene polymer (A6) was obtained in the same manner as in Example 1, except that a mixed solution of lithium amide/n-butyllithium as a polymerization initiator was supplied at 0.173 mmol/min, 2,2-bis(2-oxolanyl)propane as a polar compound was supplied at 0.037 mmol/min, c-1 as a branching agent was supplied at 0.009 mmol/min, and b-1 as a coupling modifier was supplied at 0.054 mmol/min.
• the physical properties of the modified conjugated diene polymer (A6) are shown in Table 1.
• Modified conjugated diene polymer (A7) A modified conjugated diene polymer (A7) was obtained in the same manner as in Example 1, except that a mixed solution of lithium amide/n-butyllithium as a polymerization initiator was supplied at 0.154 mmol/min, 2,2-bis(2-oxolanyl)propane as a polar compound was supplied at 0.037 mmol/min, c-1 as a branching agent was supplied at 0.009 mmol/min, and b-1 as a coupling modifier was supplied at 0.054 mmol/min.
• the physical properties of the modified conjugated diene polymer (A7) are shown in Table 1.
• Modified conjugated diene polymer (A8) A modified conjugated diene polymer (A8) was obtained in the same manner as in Example 1, except that 1,3-butadiene was supplied at 16.0 g/min, additional 1,3-butadiene was supplied at 8.6 g/min, and b-1 as a coupling modifier was supplied at 0.054 mmol/min.
• the physical properties of the modified conjugated diene polymer (A8) are shown in Table 1.
• Modified conjugated diene polymer (A9) A modified conjugated diene polymer (A9) was obtained in the same manner as in Example 1, except that 1,3-butadiene was supplied at 13.6 g/min, additional 1,3-butadiene was supplied at 11.1 g/min, and b-1 as a coupling modifier was supplied at 0.054 mmol/min.
• the physical properties of the modified conjugated diene polymer (A9) are shown in Table 1.
• Example 10 Modified conjugated diene polymer (A10) A modified conjugated diene polymer (A10) was obtained in the same manner as in Example 1, except that 1,3-butadiene was supplied at 19.7 g/min, styrene was supplied at 4.6 g/min, and 2,2-bis(2-oxolanyl)propane as a polar compound was supplied at 0.080 mmol/min.
• the physical properties of the modified conjugated diene polymer (A10) are shown in Table 1.
• Modified conjugated diene polymer (A11) A modified conjugated diene polymer (A11) was obtained in the same manner as in Example 1, except that 1,3-butadiene was supplied at 19.7 g/min, styrene at 4.6 g/min, 2,2-bis(2-oxolanyl)propane as a polar compound at 0.080 mmol/min, and b-1 as a coupling modifier at 0.044 mmol/min.
• the physical properties of the modified conjugated diene polymer (A11) are shown in Table 1.
• Modified conjugated diene polymer (A12) A modified conjugated diene polymer (A12) was obtained in the same manner as in Example 1, except that 1,3-butadiene was supplied at 19.7 g/min, styrene at 4.6 g/min, 2,2-bis(2-oxolanyl)propane as a polar compound at 0.080 mmol/min, and b-1 as a coupling modifier at 0.054 mmol/min.
• the physical properties of the modified conjugated diene polymer (A12) are shown in Table 1.
• Modified conjugated diene polymer (A13) A modified conjugated diene polymer (A13) was obtained in the same manner as in Example 1, except that 1,3-butadiene was supplied at 19.7 g/min, styrene at 4.6 g/min, 2,2-bis(2-oxolanyl)propane as a polar compound at 0.080 mmol/min, and b-1 as a coupling modifier at 0.062 mmol/min.
• the physical properties of the modified conjugated diene polymer (A13) are shown in Table 1.
• Modified conjugated diene polymer (A14) A modified conjugated diene polymer (A14) was obtained in the same manner as in Example 1, except that 1,3-butadiene was supplied at 19.7 g/min, styrene at 4.6 g/min, 2,2-bis(2-oxolanyl)propane as a polar compound at 0.080 mmol/min, and b-1 as a coupling modifier at 0.070 mmol/min.
• the physical properties of the modified conjugated diene polymer (A14) are shown in Table 1.
• Modified conjugated diene polymer (A15) A modified conjugated diene polymer (A15) was obtained in the same manner as in Example 1, except that 1,3-butadiene was supplied at 20.8 g/min, styrene at 6.9 g/min, 2,2-bis(2-oxolanyl)propane as a polar compound at 0.104 mmol/min, additional 1,3-butadiene at 6.9 g/min, c-1 as a branching agent at 0.011 mmol/min, and b-1 as a coupling modifier at 0.031 mmol/min, the temperature of the first reactor was set to 68° C., and the temperature of the second reactor was set to 70° C.
• Table 1 The physical properties of the modified conjugated diene polymer (A15) are shown in Table 1.
• Example 16 Modified conjugated diene polymer (A16) A modified conjugated diene polymer (A16) was obtained in the same manner as in Example 1, except that 1,3-butadiene was supplied at 20.8 g/min, styrene at 6.9 g/min, 2,2-bis(2-oxolanyl)propane as a polar compound at 0.104 mmol/min, additional 1,3-butadiene at 6.9 g/min, c-1 as a branching agent at 0.011 mmol/min, and b-1 as a coupling modifier at 0.044 mmol/min, the temperature of the first reactor was set to 68° C., and the temperature of the second reactor was set to 70° C.
• Table 2 The physical properties of the modified conjugated diene polymer (A16) are shown in Table 2.
• Example 17 Modified conjugated diene polymer (A17) A modified conjugated diene polymer (A17) was obtained in the same manner as in Example 1, except that 1,3-butadiene was supplied at 20.8 g/min, styrene at 6.9 g/min, 2,2-bis(2-oxolanyl)propane as a polar compound at 0.104 mmol/min, additional 1,3-butadiene at 6.9 g/min, c-1 as a branching agent at 0.011 mmol/min, and b-1 as a coupling modifier at 0.054 mmol/min, the temperature of the first reactor was set to 68° C., and the temperature of the second reactor was set to 70° C.
• Table 2 The physical properties of the modified conjugated diene polymer (A17) are shown in Table 2.
• Example 18 Modified conjugated diene polymer (A18) A modified conjugated diene polymer (A18) was obtained in the same manner as in Example 1, except that 1,3-butadiene was supplied at 20.8 g/min, styrene at 6.9 g/min, 2,2-bis(2-oxolanyl)propane as a polar compound at 0.104 mmol/min, additional 1,3-butadiene at 6.9 g/min, c-1 as a branching agent at 0.011 mmol/min, and b-1 as a coupling modifier at 0.062 mmol/min, the temperature of the first reactor was set to 68° C., and the temperature of the second reactor was set to 70° C.
• Table 2 The physical properties of the modified conjugated diene polymer (A18) are shown in Table 2.
• Modified conjugated diene polymer (A19) A modified conjugated diene polymer (A19) was obtained in the same manner as in Example 1, except that 1,3-butadiene was supplied at 20.8 g/min, styrene at 6.9 g/min, 2,2-bis(2-oxolanyl)propane as a polar compound at 0.104 mmol/min, additional 1,3-butadiene at 6.9 g/min, c-1 as a branching agent at 0.011 mmol/min, b-1 as a coupling modifier at 0.070 mmol/min, the temperature of the first reactor was set to 68° C., and the temperature of the second reactor was set to 70° C.
• Table 2 The physical properties of the modified conjugated diene polymer (A19) are shown in Table 2.
• Example 20 Modified conjugated diene polymer (A20) A modified conjugated diene polymer (A20) was obtained in the same manner as in Example 1, except that 1,3-butadiene was supplied at 16.2 g/min, styrene at 9.2 g/min, 2,2-bis(2-oxolanyl)propane as a polar compound at 0.045 mmol/min, additional 1,3-butadiene at 5.4 g/min, c-1 as a branching agent at 0.011 mmol/min, and b-1 as a coupling modifier at 0.031 mmol/min, the temperature of the first reactor was set to 68° C., and the temperature of the second reactor was set to 74° C.
• Table 2 The physical properties of the modified conjugated diene polymer (A20) are shown in Table 2.
• Example 21 Modified conjugated diene polymer (A21) A modified conjugated diene polymer (A21) was obtained in the same manner as in Example 1, except that 1,3-butadiene was supplied at 16.2 g/min, styrene at 9.2 g/min, 2,2-bis(2-oxolanyl)propane as a polar compound at 0.045 mmol/min, additional 1,3-butadiene at 5.4 g/min, c-1 as a branching agent at 0.011 mmol/min, and b-1 as a coupling modifier at 0.044 mmol/min, the temperature of the first reactor was set to 68° C., and the temperature of the second reactor was set to 74° C.
• Table 2 The physical properties of the modified conjugated diene polymer (A21) are shown in Table 2.
• Example 22 Modified conjugated diene polymer (A22) A modified conjugated diene polymer (A22) was obtained in the same manner as in Example 1, except that 1,3-butadiene was supplied at 16.2 g/min, styrene at 9.2 g/min, 2,2-bis(2-oxolanyl)propane as a polar compound at 0.045 mmol/min, additional 1,3-butadiene at 5.4 g/min, c-1 as a branching agent at 0.011 mmol/min, b-1 as a coupling modifier at 0.054 mmol/min, the temperature of the first reactor was set to 68° C., and the temperature of the second reactor was set to 74° C.
• Table 2 The physical properties of the modified conjugated diene polymer (A22) are shown in Table 2.
• Example 23 Modified conjugated diene polymer (A23) A modified conjugated diene polymer (A23) was obtained in the same manner as in Example 1, except that 1,3-butadiene was supplied at 16.2 g/min, styrene at 9.2 g/min, 2,2-bis(2-oxolanyl)propane as a polar compound at 0.045 mmol/min, additional 1,3-butadiene at 5.4 g/min, c-1 as a branching agent at 0.011 mmol/min, and b-1 as a coupling modifier at 0.062 mmol/min, the temperature of the first reactor was set to 68° C., and the temperature of the second reactor was set to 74° C.
• Table 2 The physical properties of the modified conjugated diene polymer (A23) are shown in Table 2.
• Example 24 Modified conjugated diene polymer (A24) A modified conjugated diene polymer (A24) was obtained in the same manner as in Example 1, except that 1,3-butadiene was supplied at 16.2 g/min, styrene at 9.2 g/min, 2,2-bis(2-oxolanyl)propane as a polar compound at 0.045 mmol/min, additional 1,3-butadiene at 5.4 g/min, c-1 as a branching agent at 0.011 mmol/min, and b-1 as a coupling modifier at 0.070 mmol/min, the temperature of the first reactor was set to 68° C., and the temperature of the second reactor was set to 74° C.
• Table 2 The physical properties of the modified conjugated diene polymer (A24) are shown in Table 2.
• Example 25 Modified conjugated diene polymer (A25) A modified conjugated diene polymer (A25) was obtained in the same manner as in Example 1, except that 1,3-butadiene was supplied at 17.2 g/min, styrene at 5.7 g/min, 2,2-bis(2-oxolanyl)propane as a polar compound at 0.060 mmol/min, additional 1,3-butadiene at 7.9 g/min, c-1 as a branching agent at 0.011 mmol/min, b-1 as a coupling modifier at 0.031 mmol/min, the temperature of the first reactor was set to 83° C., and the temperature of the second reactor was set to 88° C.
• Table 2 The physical properties of the modified conjugated diene polymer (A25) are shown in Table 2.
• Example 26 Modified conjugated diene polymer (A26) A modified conjugated diene polymer (A26) was obtained in the same manner as in Example 1, except that 1,3-butadiene was supplied at 17.2 g/min, styrene at 5.7 g/min, 2,2-bis(2-oxolanyl)propane as a polar compound at 0.060 mmol/min, additional 1,3-butadiene at 7.9 g/min, c-1 as a branching agent at 0.011 mmol/min, and b-1 as a coupling modifier at 0.044 mmol/min, the temperature of the first reactor was set to 83° C., and the temperature of the second reactor was set to 88° C.
• Table 2 The physical properties of the modified conjugated diene polymer (A26) are shown in Table 2.
• Example 27 Modified conjugated diene polymer (A27) A modified conjugated diene polymer (A27) was obtained in the same manner as in Example 1, except that 1,3-butadiene was supplied at 17.2 g/min, styrene at 5.7 g/min, 2,2-bis(2-oxolanyl)propane as a polar compound at 0.060 mmol/min, additional 1,3-butadiene at 7.9 g/min, c-1 as a branching agent at 0.011 mmol/min, and b-1 as a coupling modifier at 0.054 mmol/min, the temperature of the first reactor was set to 83° C., and the temperature of the second reactor was set to 88° C.
• Table 2 The physical properties of the modified conjugated diene polymer (A27) are shown in Table 2.
• Example 28 Modified conjugated diene polymer (A28) A modified conjugated diene polymer (A28) was obtained in the same manner as in Example 1, except that 1,3-butadiene was supplied at 17.2 g/min, styrene at 5.7 g/min, 2,2-bis(2-oxolanyl)propane as a polar compound at 0.060 mmol/min, additional 1,3-butadiene at 7.9 g/min, c-1 as a branching agent at 0.011 mmol/min, and b-1 as a coupling modifier at 0.062 mmol/min, the temperature of the first reactor was set to 83° C., and the temperature of the second reactor was set to 88° C.
• Table 2 The physical properties of the modified conjugated diene polymer (A28) are shown in Table 2.
• Example 29 Modified conjugated diene polymer (A29) A modified conjugated diene polymer (A29) was obtained in the same manner as in Example 1, except that 1,3-butadiene was supplied at 17.2 g/min, styrene at 5.7 g/min, 2,2-bis(2-oxolanyl)propane as a polar compound at 0.060 mmol/min, additional 1,3-butadiene at 7.9 g/min, c-1 as a branching agent at 0.011 mmol/min, and b-1 as a coupling modifier at 0.070 mmol/min, the temperature of the first reactor was set to 83° C., and the temperature of the second reactor was set to 88° C.
• Table 2 The physical properties of the modified conjugated diene polymer (A29) are shown in Table 2.
• Modified conjugated diene polymer (B1) A modified conjugated diene polymer (B1) was obtained in the same manner as in Example 1, except that n-butyllithium was used as the polymerization initiator. The physical properties of the modified conjugated diene polymer (B1) are shown in Table 3.
• Modified conjugated diene polymer (B2) A modified conjugated diene polymer (B2) was obtained in the same manner as in Example 1, except that n-butyllithium as a polymerization initiator was supplied at 0.071 mmol/min, b-1 as a coupling modifier was supplied at 0.054 mmol/min, 2,2-bis(2-oxolanyl)propane as a polar compound was supplied at 0.055 mmol/min, c-1 as a branching agent was supplied at 0.0016 mmol/min, and b-1 as a coupling modifier was supplied at 0.071 mmol/min.
• the physical properties of the modified conjugated diene polymer (B2) are shown in Table 3.
• Modified conjugated diene polymer (B4) A modified conjugated diene polymer (B4) was obtained in the same manner as in Example 1, except that n-butyllithium was used as a polymerization initiator, 1,3-butadiene was supplied at 16.2 g/min, styrene at 9.24 g/min, 2,2-bis(2-oxolanyl)propane as a polar compound at 0.104 mmol/min, additional 1,3-butadiene was supplied at 5.4 g/min, c-1 as a branching agent was supplied at 0.011 mmol/min, b-1 as a coupling modifier was supplied at 0.054 mmol/min, the temperature of the first reactor was set to 68° C., and the temperature of the second reactor was set to 70° C.
• Table 3 The physical properties of the modified conjugated diene polymer (B4) are shown in Table 3.
• Modified conjugated diene polymer (any of A1 to A29 and B1 to B4): 70 parts by mass (excluding oil) Butadiene rubber (manufactured by Ube Industries under the trade name “BR150”): 30 parts by mass; Silica (manufactured by Evonik Degussa under the trade name "Ultrasil 7000GR", nitrogen adsorption specific surface area 170 m 2 /g): 75.0 parts by mass; Carbon black (manufactured by Tokai Carbon under the trade name "Seat KH (N339)”): 5.0 parts by mass; Silane coupling agent (Evonik Degussa's product name "Si75”, bis(triethoxysilylpropyl) disulfide): 6.0 parts by mass; S-RAE oil (JX Nippon Oil & Energy Corporation's product name "Process NC140”): 32.0 parts by mass; Zinc oxide: 2.5 parts by mass; Stearic acid: 2.0 parts by mass; Antiaging agent
• a closed kneader (capacity 0.5 L) equipped with a temperature control device was used to knead modified conjugated diene polymer (either A1-A29 or B1-B4), butadiene rubber, filler (silica, carbon black), silane coupling agent, S-RAE oil, zinc oxide, and stearic acid at a filling rate of 65% and a rotor rotation speed of 30-50 rpm.
• the temperature of the closed kneader was controlled to obtain each rubber composition (compound) so that the discharge temperature was 155-160°C.
• the compound obtained above was cooled to room temperature, and then an antioxidant was added, and the compound was kneaded again under the same conditions as in the first stage of kneading to improve the dispersion of silica.
• the temperature of the mixer was controlled so that the discharge temperature of the compound was 155 to 160°C.
• sulfur and vulcanization accelerators 1 and 2 were added and kneaded with an open roll set at 70°C.
• the compound 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 performed by the following methods. The evaluation results are shown in Tables 4 to 7.
• Viscoelastic parameters fuel economy and wet grip
• the viscoelastic parameters were measured in torsion mode using a viscoelasticity tester "ARES" manufactured by Rheometrics Scientific. Each measured value was indexed with the result for the rubber composition of Comparative Example 1 being 100.
• tan ⁇ measured at 50 ° C., frequency 10 Hz, and strain 3% was used as an index of low hysteresis loss, i.e., fuel saving
• the result of Comparative Example 1 was standardized as 100. The larger the index, the better the fuel saving, and those with such a value exceeding 65 were evaluated as having excellent fuel saving.
• the modified conjugated diene polymer of the present invention has excellent bale moldability, processability, and fuel saving performance.
• the vulcanizate thereof has an excellent balance of performance in terms of abrasion resistance, fracture properties, and low hysteresis loss.
• the modified conjugated diene polymer, the manufacturing method for the modified conjugated diene polymer, the modified conjugated diene polymer composition, the rubber composition, etc. of the present invention have excellent moldability of the modified conjugated diene polymer, and the vulcanizate thereof has an excellent balance of performance such as abrasion resistance, fracture characteristics, and low hysteresis loss, and therefore have industrial applicability in applications such as tires, resin modification, interior and exterior parts of automobiles, anti-vibration rubber, and footwear.

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