WO2016133202A1 - 変性共役ジエン系重合体及びその製造方法、並びに変性共役ジエン系重合体組成物 - Google Patents
変性共役ジエン系重合体及びその製造方法、並びに変性共役ジエン系重合体組成物 Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- 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
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- 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
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
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- 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
- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
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- 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
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- 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
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/544—Silicon-containing compounds containing nitrogen
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- 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
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/544—Silicon-containing compounds containing nitrogen
- C08K5/5445—Silicon-containing compounds containing nitrogen containing at least one Si-N bond
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- 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
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/544—Silicon-containing compounds containing nitrogen
- C08K5/5477—Silicon-containing compounds containing nitrogen containing nitrogen in a heterocyclic ring
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L47/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds; Compositions of derivatives of such polymers
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- 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
- C08L9/06—Copolymers with styrene
Definitions
- the present invention relates to a modified conjugated diene polymer, a method for producing the same, and a modified conjugated diene polymer composition.
- a rubber composition that uses silica as a reinforcing filler used in the rubber material. Further, there is a rubber composition using a diene rubber having a functional group that interacts with the surface of silica, and the diene rubber has a high affinity with the surface of silica. The dispersibility of the silica is good, and excellent low heat build-up can be obtained.
- Patent Document 1 discloses a modified diene rubber obtained by reacting a polymer terminus with a modifier having a glycidylamino group
- Patent Document 2 discloses glycidoxyalkoxysilane as a polymer terminal.
- a modified diene rubber obtained by reacting with discloses a modified diene rubber obtained by reacting with.
- Patent Documents 3 and 4 disclose a modified diene rubber obtained by reacting an alkoxysilane containing an amino group with a polymer terminal, and a composition of these with silica.
- Patent Document 5 discloses a diene rubber obtained by a coupling reaction between a polymer active terminal and a polyfunctional silane compound.
- a rubber composition obtained by blending silica having a hydrophilic surface with a highly hydrophobic diene rubber has poor dispersibility due to aggregation of silica particles.
- a modified diene rubber having a functional group highly reactive with silica introduced at a polymerization terminal is blended with silica to obtain a rubber composition, kneading is performed. During the process, the reaction between the silica particles and the functional group of the modified diene rubber proceeds.
- the rubber composition has deteriorated processability such as difficulty in kneading due to an increase in viscosity, and rough skin or sheet breakage when forming a sheet after kneading.
- processability such as difficulty in kneading due to an increase in viscosity, and rough skin or sheet breakage when forming a sheet after kneading.
- steering stability is deteriorated due to a decrease in rigidity or dynamic elastic modulus.
- such a vulcanizate does not have a sufficient balance between low hysteresis loss and wet skid resistance.
- the present invention is excellent in workability when it is a vulcanized product, and is excellent in balance between low hysteresis loss and wet skid resistance when used as a vulcanized product, and fracture strength and wear resistance.
- An object is to provide a modified conjugated diene polymer.
- the modified conjugated diene copolymer having a Mooney relaxation rate and a modification rate within a specific range is a vulcanized product.
- the present inventors have found that it is excellent in workability and has excellent balance between low hysteresis loss property and wet skid resistance when used as a vulcanizate, as well as fracture strength and wear resistance, and has completed the present invention.
- the present invention is as follows. [1] Mooney relaxation rate measured at 110 ° C. is 0.45 or less, A modified conjugated diene polymer having a modification rate of 75% by mass or more. [2] Have a nitrogen atom, The modified conjugated diene polymer according to [1], wherein a content of the nitrogen atom is 25 mass ppm or more based on a total amount of the modified conjugated diene polymer. [3] Having a nitrogen atom at least at one end; The modified conjugated diene polymer according to [1] or [2], which has a star-shaped polymer structure centered on a nitrogen atom-containing alkoxysilane substituent.
- R 21 to R 24 each independently represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms
- R 25 and R 26 each independently represent Represents an alkylene group having 1 to 20 carbon atoms
- R 27 represents a hydrogen atom, a silyl group substituted with a hydrocarbon, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms.
- c each independently represents an integer of 1 or 2
- b and d each independently represents an integer of 0 or 1
- (a + b) and (c + d) each independently represents 2
- (Polym) represents a conjugated diene compound, or a conjugated diene polymer obtained by polymerizing or copolymerizing a conjugated diene compound and an aromatic vinyl compound, and at least one terminal thereof is Represented by any of the following general formulas (4) to (7) R 21 in the case of.
- R 28 to R 33 each independently represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms
- R 34 to R 36 each independently represents Represents an alkylene group having 1 to 20 carbon atoms
- a, c and e each independently represent an integer of 1 or 2
- b, d and f each independently represent 0 or 1
- Represents an integer, (a + b), (c + d), and (e + f) each independently represents an integer of 2 or less
- (Polym) represents a conjugated diene compound, or a conjugated diene compound and an aromatic vinyl compound.
- R 28, R 30, and R 32, and there are a plurality (Pol m) are each independently.
- R 10 and R 11 are each independently a group consisting of an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 14 carbon atoms, and an aralkyl group having 6 to 20 carbon atoms.
- R 10 and R 11 may be bonded to form a cyclic structure with an adjacent nitrogen atom, in which case R 10 and R 11 have 5 to 12 carbon atoms Represents an alkyl group, and a part thereof may have an unsaturated bond or a branched structure.
- R 12 and R 13 are each independently a group consisting of an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 14 carbon atoms, and an aralkyl group having 6 to 20 carbon atoms.
- R 12 and R 13 may be bonded to form a cyclic structure with an adjacent nitrogen atom, and in this case, R 12 and R 13 each have 5 to 12 carbon atoms.
- R 14 represents an alkyl group, which may have an unsaturated bond or a branched structure at a part thereof, and R 14 represents an alkylene group having 1 to 20 carbon atoms or a conjugated diene polymer having 1 to 20 carbon atoms.
- R 15 and R 16 are each independently a group consisting of an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 14 carbon atoms, and an aryl group having 6 to 20 carbon atoms.
- R 15 and R 16 may be bonded to form a cyclic structure with an adjacent nitrogen atom, and in this case, R 15 and R 16 have 5 to 12 carbon atoms.
- An alkyl group is shown, and a part thereof may have a branched structure.
- R 17 represents a hydrocarbon group having 2 to 10 carbon atoms, and a part thereof may have an unsaturated bond or a branched structure.
- R 18 has 1 to 12 carbon atoms.
- R 1 to R 4 each independently represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms
- R 5 represents an alkylene having 1 to 10 carbon atoms
- R 6 represents an alkylene group having 1 to 20 carbon atoms
- m represents an integer of 1 or 2
- n represents an integer of 2 or 3
- (m + n) represents an integer of 4 or more.
- R 1 to R 6 each independently represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms
- R 7 to R 9 each independently represents Represents an alkylene group having 1 to 20 carbon atoms
- m, n and l each independently represents an integer of 1 to 3
- (m + n + 1) represents an integer of 4 or more.
- R 1 to R 6 are independent of each other.
- R 1 to R 4 each independently represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms
- R 5 and R 6 are each independently Represents an alkylene group having 1 to 20 carbon atoms
- m and n each independently represents an integer of 1 to 3
- (m + n) represents an integer of 4 or more
- R 7 represents 1 carbon atom.
- the modifying agent includes a modifying agent represented by the formula (1), and m in the formula (1) represents 2 and n represents 3, or the modification represented by the formula (2).
- R 10 and R 11 are each independently a group consisting of an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 14 carbon atoms, and an aralkyl group having 6 to 20 carbon atoms.
- R 10 and R 11 may be bonded to form a cyclic structure with an adjacent nitrogen atom, in which case R 10 and R 11 have 5 to 12 carbon atoms Represents an alkyl group, and a part thereof may have an unsaturated bond or a branched structure.
- R 12 and R 13 are each independently a group consisting of an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 14 carbon atoms, and an aralkyl group having 6 to 20 carbon atoms.
- R 12 and R 13 may be bonded to form a cyclic structure with an adjacent nitrogen atom, and in this case, R 12 and R 13 each have 5 to 12 carbon atoms.
- R 14 represents an alkyl group, which may have an unsaturated bond or a branched structure at a part thereof, and R 14 represents an alkylene group having 1 to 20 carbon atoms or a conjugated diene polymer having 1 to 20 carbon atoms.
- R 15 and R 16 are each independently a group consisting of an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 14 carbon atoms, and an aryl group having 6 to 20 carbon atoms.
- R 15 and R 16 may be bonded to form a cyclic structure with an adjacent nitrogen atom, and in this case, R 15 and R 16 have 5 to 12 carbon atoms.
- An alkyl group is shown, and a part thereof may have a branched structure.
- R 17 represents a hydrocarbon group having 2 to 10 carbon atoms, and a part thereof may have an unsaturated bond or a branched structure.
- R 18 has 1 to 12 carbon atoms. And may have a branched structure in a part thereof.
- the polymerization temperature is 45 ° C. or more and 80 ° C.
- a method for producing a modified conjugated diene polymer [14] In any one of [9] to [13], in the polymerization step, the polymerization method is continuous, and the concentration of the organolithium compound is 0.010 mol / L or less with respect to the volume of the hydrocarbon solvent. A process for producing the modified conjugated diene polymer as described. [15] In the modification step, the content of the conjugated diene compound is 100 mass ppm or more and 50000 mass ppm or less based on the total amount of the monomer and the polymer, according to any one of [9] to [14]. A method for producing a modified conjugated diene polymer.
- [16] [Modified conjugated diene polymer obtained by the method for producing a modified conjugated diene polymer according to any one of [9 to [15].
- [17] A rubber component, and 0.5 to 300 parts by mass of a silica-based inorganic filler with respect to 100 parts by mass of the rubber component, The rubber component contains 20 parts by mass or more of the modified conjugated diene polymer according to any one of [1] to [8] and [16] with respect to 100 parts by mass of the rubber component. Combined composition.
- the modified conjugated diene polymer according to the present invention excellent workability when making a vulcanized product, and a balance between excellent low hysteresis loss and wet skid resistance when using a vulcanized product, Excellent fracture strength and wear resistance can be obtained.
- the present embodiment a mode for carrying out the present invention (hereinafter referred to as “the present embodiment”) will be described in detail.
- the following embodiments are examples for explaining the present invention, and are not intended to limit the present invention to the following contents.
- the present invention can be implemented with appropriate modifications within the scope of the gist thereof.
- the modified conjugated diene polymer of the present embodiment has a Mooney relaxation rate (hereinafter also referred to simply as “Mooney relaxation rate” or “MSR”) measured at 110 ° C. of 0.45 or less, and the modification rate is 75% by mass or more.
- Mooney relaxation rate hereinafter also referred to simply as “Mooney relaxation rate” or “MSR”
- the Mooney relaxation rate measured at 110 ° C. of the modified conjugated diene polymer is an indicator of the branched structure and molecular weight of the modified conjugated diene copolymer.
- the Mooney relaxation rate at 110 ° C. of the modified conjugated diene polymer is 0.45 or less, preferably 0.42 or less, more preferably 0.40 or less, and 0.38 or less. Is more preferable, and it is still more preferable that it is 0.35 or less.
- the lower limit of the Mooney relaxation rate is not particularly limited and may be a detection limit value or less, but is preferably 0.05 or more. When the Mooney relaxation rate is 0.45 or less, the effect of the present embodiment is exhibited.
- the MSR measured at 110 ° C. of the modified conjugated diene polymer is an indicator of the molecular weight and the number of branches of the modified conjugated diene polymer.
- the molecular weight and the number of branches of the modified conjugated diene polymer (for example, the number of branches of a star polymer (also referred to as “number of arms of a star polymer”)) tend to increase. is there.
- the MSR in this case may be used as an index of the degree of branching. it can.
- MSR is measured using a Mooney viscometer as follows.
- the measurement temperature of the Mooney relaxation rate is 110 ° C.
- the rotor is rotated at 2 rpm, the torque after 4 minutes is measured, and the measured value is taken as the Mooney viscosity (ML (1 + 4)).
- the rotation of the rotor is stopped immediately, the torque every 0.1 second from 1.6 seconds to 5 seconds is recorded in Mooney units, and the torque and time (seconds) are plotted on the logarithmic plot.
- the slope is obtained and the absolute value is taken as the Mooney relaxation rate (MSR). More specifically, it measures by the method as described in the Example mentioned later.
- the weight average molecular weight of the modified conjugated diene polymer is 700,000 or more and the degree of branching is 3 or more, or the weight average molecular weight of the modified conjugated diene polymer is If it is 650000 or more and the branching degree is 4 or more, it tends to be 0.45 or less.
- the weight average molecular weight of the modified conjugated diene polymer is 750,000 or more and the degree of branching is 3 or more, or the weight average of the modified conjugated diene polymer.
- the degree of branching can be controlled by, for example, the number of functional groups of the modifier, the amount of modifier added, or the degree of metallation progression.
- the modified conjugated diene-based copolymer of the present embodiment has a Mooney viscosity measured at 110 ° C. of 100 or more from the viewpoint of processability when used as a vulcanized product and wear resistance when used as a vulcanized product. It is preferably 200 or less, more preferably 110 or more and 180 or less, and further preferably 120 or more and 160 or less.
- the Mooney viscosity is measured by the method described in Examples described later.
- the Mooney relaxation rate is 0.45 or less, and the modification rate is 75% by mass or more. More preferably, the Mooney relaxation rate is 0.45 or less and the modification rate is 78% by mass or more. More preferably, the Mooney relaxation rate is 0.44 or less and the modification rate is 80% by mass or more. More preferably, the Mooney relaxation rate is 0.43 or less and the modification rate is 85% by mass or more, and even more preferably, the Mooney relaxation rate is 0.42 or less and the modification rate is 88. More preferably, the Mooney relaxation rate is 0.40 or less, and the modification rate is 90% by mass or more.
- an organic lithium compound having at least one nitrogen atom in the molecule is polymerized.
- examples thereof include a method of using a modifier that is used as an initiator and further gives a specific branching rate after polymerization.
- an organolithium compound having at least one nitrogen atom in the molecule is used as a polymerization initiator for polymerization, the chain transfer reaction is promoted and a low molecular weight product having a deactivated polymerization active terminal is generated. Due to this, the modification rate becomes small.
- a modification rate (a polymer having a specific functional group (for example, a polymer having a nitrogen atom at a polymerization initiation terminal and / or a formula (1) or (2) described later) is used.
- the amount of the modified conjugated diene polymer modified with a modifying agent is 75% by mass or more, preferably 78% by mass or more, more preferably 80% by mass or more, further preferably 85% by mass or more, and still more. It is preferable to produce the modified conjugated diene polymer that is preferably 88% by mass or more, and more preferably 90% by mass or more.
- the modification rate can be measured by chromatography capable of separating a functional group-containing modified component and a non-modified component.
- chromatography capable of separating a functional group-containing modified component and a non-modified component.
- a column for gel permeation chromatography using a polar substance such as silica adsorbing a specific functional group as a packing material is used, and the internal standard of the non-adsorbing component is used for comparison.
- a method is mentioned. More specifically, the denaturation rate is determined by the adsorption of the sample solution containing the sample and the low molecular weight internal standard polystyrene to the silica column from the difference between the chromatogram measured with the polystyrene gel column and the chromatogram measured with the silica column. Measure the amount. More specifically, the modification rate is measured by the method described in the examples.
- the modified conjugated diene polymer of the present embodiment has a nitrogen atom, and the nitrogen atom content (hereinafter referred to as “nitrogen content test method”) measured by oxidative combustion-chemiluminescence method (JIS-2609: crude oil and crude oil product—nitrogen content test method). Simply referred to as “nitrogen content”) is preferably 25 ppm by mass or more based on the total amount of the modified conjugated diene polymer.
- the nitrogen content of the modified conjugated diene polymer is preferably 25 mass ppm or more with respect to the total amount of the modified conjugated diene polymer, from the viewpoint of making the effect of the present embodiment more excellent. More preferably, it is 40 mass ppm or more, more preferably 50 mass ppm or more, still more preferably 60 mass ppm or more, and preferably 500 mass ppm or less, and 400 mass ppm or less. It is more preferable that it is 300 mass ppm or less, and it is more preferable that it is 250 mass ppm or less. More specifically, the nitrogen atom content is measured by the method described in the examples described later.
- a modified conjugated diene polymer having a nitrogen content of 25 mass ppm or more for example, a continuous polymerization of a conjugated diene polymer using an organolithium compound having at least one nitrogen atom in the molecule as a polymerization initiator. Then, a method of reacting a modifying agent having at least one nitrogen atom in the molecule can be mentioned.
- a polymerization initiator that is an organolithium compound having at least one nitrogen atom in the molecule, and at least in the molecule
- examples thereof include a method of polymerizing and modifying a conjugated diene polymer having a number average molecular weight of 100,000 or less in combination with a modifier having one nitrogen atom.
- the modified conjugated diene-based polymer of the present embodiment has a shrinkage factor (g ′) (hereinafter, simply referred to as “shrinkage factor (g ′)” or a gel permeation chromatography with viscosity detector (GPC) -light scattering measurement. (Also referred to as “shrinking factor”) is preferably 0.86 or less.
- the shrinkage factor (g ′) is an indicator of the branched structure of the modified conjugated diene copolymer.
- the shrinkage factor (g ′) of the modified conjugated diene polymer is preferably 0.86 or less, more preferably 0.81 or less, and even more preferably 0.77 or less.
- the lower limit of the contraction factor (g ′) is not particularly limited and may be not more than the detection limit value, but is preferably not less than 0.02. When the contraction factor (g ′) is 0.81 or less, the effect of the present embodiment is more reliably expressed.
- a modifier having four or more reaction points with the living active terminal is added to the total number of moles of the polymerization initiator.
- a method of adding a mole number of 1/3 or less that is, obtaining a modified conjugated diene copolymer having three or more branches.
- the shrinkage factor (g ′) measured by GPC-light scattering measurement with a viscosity detector (hereinafter also simply referred to as “GPC-light scattering measurement with viscosity detector” or “3D-GPC measurement”) is It also serves as an index of the number of branches of the modified conjugated diene polymer.
- the number of branches of the modified conjugated diene polymer for example, the number of branches of a star polymer (also referred to as “number of arms of a star polymer”.
- the shrinkage factor (g ′) decreases as the number of branches of the modified conjugated diene polymer increases. It can be used as an index of the degree of branching.
- Contractile factor (g ′) is measured using 3D-GPC measurements.
- the range of M was input from 1000 to 20000000, and the relationship between the standard intrinsic viscosity [ ⁇ ] 0 and the molecular weight M was created, with respect to the standard intrinsic viscosity [ ⁇ ] 0 , the sample obtained by 3D-GPC measurement
- the intrinsic viscosity [ ⁇ ] at each molecular weight M is calculated as [ ⁇ ] / [ ⁇ ] 0 at each molecular weight M as the relationship of the intrinsic viscosity [ ⁇ ] with respect to the standard intrinsic viscosity [ ⁇ ] 0 , and the average value thereof is a shrinkage factor ( More specifically, it is measured by the method described
- the modified conjugated diene polymer preferably has a star polymer structure having a nitrogen atom at at least one terminal and centering on a nitrogen-containing alkoxysilane substituent.
- a nitrogen atom at at least one terminal for example, in the polymerization step described in the production method described later, there is a tendency that it can be achieved by using a polymerization initiator containing nitrogen.
- the nitrogen-containing alkoxysilane preferably has a structure derived from a modifier.
- the “star-shaped polymer structure” in the present specification is a structure in which a plurality of linear molecular chains (arms) are bonded from one branch point.
- one branching point here is bonded to a linear molecular chain containing at least a nitrogen atom and a linear molecular chain containing an alkoxysilane group.
- the modified conjugated diene polymer of the present embodiment has a second number determined by GPC-light scattering measurement with respect to a first number average molecular weight (Mn) in terms of polystyrene determined by gel permeation chromatography (GPC).
- Mn number average molecular weight
- the average molecular weight (Mn-i) is preferably 1.00 or more, more preferably 1.20 or more, and further preferably 1.30 or more.
- the first number average molecular weight is a polystyrene-equivalent number average molecular weight obtained by gel permeation chromatography (GPC) measurement, and is a relative molecular weight.
- the relative molecular weight is affected by the rotation radius of the polymer to be measured.
- the second number average molecular weight is a number average molecular weight measured by GPC-light scattering measurement, and is an absolute molecular weight.
- the absolute molecular weight is not affected by the turning radius of the polymer. Therefore, the second number average molecular weight (Mn-i / Mn) with respect to the first number average molecular weight is an index of the branched structure and molecular weight of the polymer.
- (Mn-i / Mn) when (Mn-i / Mn) is 1.00 or more, the molecular weight is high and the structure has a branched structure.
- the upper limit of (Mn-i / Mn) is not particularly limited, but is preferably 3.00 or less.
- the modified conjugated diene polymer of the present embodiment has a second weight determined by GPC-light scattering measurement with respect to a first weight average molecular weight (Mw) in terms of polystyrene determined by gel permeation chromatography (GPC).
- Mw weight average molecular weight
- the average molecular weight (Mw-i) is preferably 1.00 or more, more preferably 1.02 or more, and further preferably 1.05 or more.
- the first weight average molecular weight is a polystyrene equivalent weight average molecular weight obtained by gel permeation chromatography (GPC) measurement, and is a relative molecular weight.
- the relative molecular weight is affected by the rotation radius of the polymer to be measured.
- the second weight average molecular weight is obtained by GPC-light scattering measurement, and the obtained weight average molecular weight is an absolute molecular weight.
- the absolute molecular weight is not affected by the turning radius of the polymer. Therefore, the second number average molecular weight (Mw ⁇ i / Mw) with respect to the first number average molecular weight is an index of the branched structure and molecular weight of the polymer.
- (Mw ⁇ i / Mw) when (Mw ⁇ i / Mw) is 1.00 or more, the molecular weight is high and the structure has a branched structure.
- the upper limit of (Mw ⁇ i / Mw) is not particularly limited, but is preferably 2.00 or less.
- the first number average molecular weight (Mn) is preferably 200000 or more and 200000 or less, and 250,000 or more and 1500,000 or less, from the viewpoint of a balance between performance and processing characteristics. Is more preferable, and it is more preferable that it is 300000 or more and 1000000 or less.
- the strength of the vulcanized product tends to be further improved. Tends to be further improved.
- the modified conjugated diene polymer of the present embodiment preferably has a first weight average molecular weight of 400,000 or more and 4000000 or less, more preferably 500,000 or more and 3000000 or less, from the viewpoint of a balance between performance and processability. Preferably, it is 600000 or more and 200000 or less.
- the first weight average molecular weight (Mw) (Mw / Mn) with respect to the first number average molecular weight (Mn) of the modified conjugated diene polymer of the present embodiment is preferably 1 from the viewpoint of physical properties of the vulcanizate. It is 0.000 or more and 3.50 or less, More preferably, it is 1.50 or more and 3.40 or less, More preferably, it is 1.60 or more and 2.70 or less, More preferably, it is 1.70 or more and 2.50 or less. It is. Moreover, it is more preferable that 1st number average molecular weight (Mn) is 200000 or more and 2000000 or less, and (Mw / Mn) is 1.50 or more and 3.50 or less.
- the modified conjugated diene polymer of the present embodiment is preferably a modified conjugated diene polymer represented by the following general formula (A) or (B).
- R 21 to R 24 each independently represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms
- R 25 and R 26 each independently represent R 1 represents an alkylene group having 1 to 20 carbon atoms
- R 27 represents a hydrogen atom, a silyl group substituted with a hydrocarbon, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms.
- a and c each independently represent an integer of 1 or 2
- b and d each independently represent an integer of 0 or 1
- (a + b) and (c + d) are each independently Represents an integer of 2 or less
- (Polym) represents a conjugated diene compound, or a conjugated diene polymer obtained by polymerizing or copolymerizing a conjugated diene compound and an aromatic vinyl compound, and at least one terminal thereof is Represents a functional group represented by any one of the following general formulas (4) to (7).
- the modified conjugated diene polymer may have, for example, in the modified conjugated diene polymer represented by the formula (A), the Si atom bonded to R 25 is branched.
- the point include a structure in which the branch point is bonded to a linear molecular chain (arm), R 25 , (OR 21 ) 3-ab , R 22 b , and (Polym) a .
- R 28 to R 33 each independently represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms
- R 34 to R 36 are each independently An alkylene group having 1 to 20 carbon atoms
- a, c, and e each independently represent an integer of 1 or 2
- b, d, and f each independently represent an integer of 0 or 1
- e + f) each independently represents an integer of 2 or less
- (Polym) is a conjugated diene compound, or a conjugated diene system obtained by polymerizing or copolymerizing a conjugated diene compound and an aromatic vinyl compound.
- R 28 , R 30 , and R 32 and a plurality of (Polym) in the case where a plurality exist are independent of each other.
- Examples of the above-described star-shaped polymer structure that the modified conjugated diene polymer may have include, for example, a branched Si atom bonded to R 34 in the modified conjugated diene polymer represented by the formula (B).
- Examples of the point include a structure in which the branch point is bonded to linear molecular chains (arms) R 34 , (OR 28 ) 3-ab , R 29 b , and (Polym) a .
- R 10 and R 11 are each independently selected from the group consisting of an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 14 carbon atoms, and an aralkyl group having 6 to 20 carbon atoms. At least one selected is shown.
- R 10 and R 11 may be bonded to form a cyclic structure with the adjacent nitrogen atom.
- R 10 and R 11 represent an alkyl group having 5 to 12 carbon atoms, It may have a saturated bond or a branched structure.
- R 12 and R 13 are each independently selected from the group consisting of an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 14 carbon atoms, and an aralkyl group having 6 to 20 carbon atoms. At least one selected is shown.
- R 12 and R 13 may be bonded to form a cyclic structure with an adjacent nitrogen atom.
- R 12 and R 13 represent an alkyl group having 5 to 12 carbon atoms, and a part thereof is It may have a saturated bond or a branched structure.
- R 14 represents an alkylene group having 1 to 20 carbon atoms or a conjugated diene polymer having 1 to 20 carbon atoms.
- R 15 and R 16 are each independently selected from the group consisting of an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 14 carbon atoms, and an aryl group having 6 to 20 carbon atoms. At least one selected is shown.
- R 15 and R 16 may be bonded to form a cyclic structure with an adjacent nitrogen atom, in which case R 15 and R 16 represent an alkyl group having 5 to 12 carbon atoms, and branched into a part thereof. You may have a structure.
- R 17 forms a cyclic structure with a nitrogen atom, represents an alkyl group having 2 to 12 carbon atoms in total, and may have an unsaturated bond or a branched structure in a part thereof.
- R 18 represents an alkyl group having 1 to 12 carbon atoms, and a part thereof may have a branched structure.
- R 21 to R 24 each independently preferably represents an alkyl group having 1 to 8 carbon atoms, and more preferably represents an alkyl group having 1 to 4 carbon atoms.
- R 25 and R 26 each independently preferably represents an alkylene group having 1 to 8 carbon atoms, and more preferably represents an alkylene group having 2 to 4 carbon atoms.
- R 27 preferably represents a hydrogen atom or an alkyl group having 0 to 6 carbon atoms, and more preferably represents a hydrogen atom.
- examples of R 21 to R 24 are not limited to the following, but examples include a methyl group, an ethyl group, a propyl group, a butyl group, and an isobutyl group, preferably a methyl group and an ethyl group. It is.
- examples of R 25 and R 26 include a methylene group, an ethylene group, a propylene group, a butylene group, and a pentylene group, and an ethylene group, a propylene group, and a butylene group are preferable.
- R 27 examples include a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, and an isobutyl group, and a hydrogen atom, a methyl group, and an ethyl group are preferable.
- the number average molecular weight of (Polym) is not particularly limited, but is preferably 250,000 or more and 1500,000 or less, and more preferably 350,000 or more and 900,000 or less.
- R 28 to R 33 each independently preferably represents an alkyl group having 1 to 8 carbon atoms, and more preferably represents an alkyl group having 1 to 4 carbon atoms.
- R 34 to R 36 each independently represents an alkylene group having 1 to 8 carbon atoms, and more preferably an alkylene group having 2 to 4 carbon atoms.
- Examples of R 28 to R 33 include a methyl group, an ethyl group, a propyl group, a butyl group, and an isobutyl group, and a methyl group and an ethyl group are preferable.
- R 34 to R 36 examples include a methylene group, an ethylene group, a propylene group, a butylene group, and a pentylene group, and an ethylene group, a propylene group, and a butylene group are preferable.
- the number average molecular weight of (Polym) is not particularly limited, but is preferably 250,000 or more and 1500,000 or less, and more preferably 350,000 or more and 900,000 or less.
- R 10 and R 11 when R 10 and R 11 represent an alkyl group, R 10 and R 11 preferably represent an alkyl group having 1 to 6 carbon atoms. When R 10 and R 11 represent a cycloalkyl group, R 10 and R 11 preferably represent a cycloalkyl group having 5 to 7 carbon atoms. When R 10 and R 11 represent an aralkyl group, R 10 and R 11 preferably represent an aralkyl group having 6 to 8 carbon atoms. When R 10 and R 11 are bonded to form a cyclic structure with an adjacent nitrogen atom, R 10 and R 11 preferably represent an alkyl group having 5 to 7 carbon atoms.
- R 10 and R 11 are not limited to the following, but include, for example, a methyl group, an ethyl group, a propyl group, a butyl group, and an isobutyl group, and preferably a butyl group and an isobutyl group. It is.
- R 10 and R 11 are bonded to form a cyclic structure together with the adjacent nitrogen atom
- the examples of R 10 and R 11 are not limited to the following, but include, for example, a methylene group, ethylene Group, a propylene group, a butylene group, a pentylene group, and a hexylene group, and a butylene group, a pentylene group, and a hexylene group are preferable.
- R 12 and R 13 when R 12 and R 13 are bonded to form a cyclic structure with the adjacent nitrogen atom, R 12 and R 13 may represent an alkyl group having 1 to 8 carbon atoms. preferable.
- R 12 and R 13 are not limited to the following, but include, for example, a methyl group, an ethyl group, a propyl group, a butyl group, and an isobutyl group, and preferably a butyl group and an isobutyl group. It is a group.
- R 12 and R 13 are bonded to form a cyclic structure together with the adjacent nitrogen atom
- the examples of R 12 and R 13 are not limited to the following, but include, for example, a methylene group, ethylene Group, a propylene group, a butylene group, a pentylene group, and a hexylene group, and a butylene group, a pentylene group, and a hexylene group are preferable.
- R 14 preferably represents an alkylene group having 1 to 8 carbon atoms.
- R 14 are not limited to the following, but examples include methylene group, ethylene group, propylene group, butylene group, pentylene group, and hexylene group, preferably ethylene group, propylene And a butylene group.
- R 15 and R 16 indicate, but are not limited to, for example, a methyl group, an ethyl group, a propyl group, a butyl group, and an isobutyl group, and preferably a methyl group Group and ethyl group.
- R 17 preferably represents a total alkyl group having 4 to 6 carbon atoms.
- R 18 preferably represents an alkyl group having 1 to 4 carbon atoms.
- what R17 shows is not limited to the following, but examples include a butylene group, a pentylene group, and a hexylene group, and a pentylene group and a hexylene group are preferable.
- Examples of R 18 are not limited to the following, but examples include a methyl group, an ethyl group, a propyl group, a butyl group, and an isobutyl group, and a methyl group and an ethyl group are preferable.
- the modified conjugated diene polymer of the present embodiment includes a polymerization step in which an organic lithium compound having at least one nitrogen atom in the molecule is used as a polymerization initiator, and at least a conjugated diene compound is polymerized to obtain a conjugated diene polymer.
- a modified step of modifying the conjugated diene polymer with a modifier having four or more alkoxy groups bonded to a silyl group in one molecule and a tertiary amino group It is obtained by a method for producing a coalescence.
- the conjugated diene polymer constituting the modified conjugated diene polymer is a homopolymer of a single conjugated diene compound, a polymer or copolymer of different types of conjugated diene compounds, or a conjugated diene compound and an aromatic vinyl compound. And a copolymer.
- the polymerization initiator of the present embodiment uses an organolithium compound having at least one nitrogen atom in the molecule, or a polymerization initiator system containing a compound having at least one nitrogen atom in the molecule and an organolithium compound. Can do.
- an organolithium compound having at least one nitrogen atom in the molecule may be prepared in a predetermined reactor in advance, or in a reactor for performing polymerization or copolymerization described later.
- the compound having at least one nitrogen atom in the molecule and organolithium may be reacted simultaneously with or before the polymerization or copolymerization.
- R 10 and R 11 are each independently selected from the group consisting of an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 14 carbon atoms, and an aralkyl group having 6 to 20 carbon atoms. At least one selected is shown.
- R 10 and R 11 may be bonded to form a cyclic structure with the adjacent nitrogen atom.
- R 10 and R 11 represent an alkyl group having 5 to 12 carbon atoms, It may have a saturated bond or a branched structure.
- R 12 and R 13 are each independently selected from the group consisting of an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 14 carbon atoms, and an aralkyl group having 6 to 20 carbon atoms. At least one selected is shown.
- R 12 and R 13 may be bonded to form a cyclic structure with an adjacent nitrogen atom.
- R 12 and R 13 represent an alkyl group having 5 to 12 carbon atoms, and a part thereof is It may have a saturated bond or a branched structure.
- R 14 represents an alkylene group having 1 to 20 carbon atoms or a conjugated diene polymer having 1 to 20 carbon atoms.
- X represents a Cl atom, a Br atom, or an I atom.
- R 15 and R 16 are each independently selected from the group consisting of an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 14 carbon atoms, and an aryl group having 6 to 20 carbon atoms. At least one selected is shown. R 15 and R 16 may be bonded to form a cyclic structure with an adjacent nitrogen atom, in which case R 15 and R 16 represent an alkyl group having 5 to 12 carbon atoms, and branched into a part thereof. May have structure
- R 10 and R 11 indicate, but are not limited to, for example, methyl group, ethyl group, propyl group, butyl group, octyl group, cyclopropyl group, cyclohexyl group, 3- Examples include phenyl-1-propyl group, isobutyl group, decyl group, heptyl group, and phenyl group.
- the compound represented by the formula (24) is not limited to the following, but examples include dimethylamine, diethylamine, dibutylamine, dipropylamine, diheptylamine, dihexylamine, dioctylamine, di-2-ethyl.
- Examples include hexylamine, didecylamine, ethylpropylamine, ethylbutylamine, ethylbenzylamine, and methylphenethylamine.
- the compound represented by the formula (24) is not limited to these, and includes the similar compounds as long as the above conditions are satisfied.
- the compound represented by the formula (24) is used to reduce hysteresis loss of the modified conjugated diene polymer composition described later, reduce unpleasant odor of the modified conjugated diene polymer described later, and control the chain transfer reaction described later. From the viewpoint, dibutylamine and dihexylamine are preferable, and dibutylamine is more preferable.
- the compound represented by the formula (24) includes piperidine, hexamethyleneimine, azacyclooctane, 1,3, Examples include 3-trimethyl-6-azabicyclo [3.2.1] octane, 1,2,3,6-tetrahydropyridine, and 3,5-dimethylpiperidine.
- the compound represented by the formula (24) is not limited to these, and includes the similar compounds as long as the above conditions are satisfied.
- the compound represented by the formula (24) is used to reduce hysteresis loss of the modified conjugated diene polymer composition described later, reduce unpleasant odor of the modified conjugated diene polymer described later, and control the chain transfer reaction described later.
- piperidine, hexamethyleneimine, azacyclooctane, 1,3,3-trimethyl-6-azabicyclo [3.2.1] octane, and 3,5-dimethylpiperidine are preferable, and piperidine, hexamethylene are more preferable.
- R 14 preferably represents an alkyl group having 2 to 16 carbon atoms, more preferably 3 carbon atoms from the viewpoint of reactivity and interaction with an inorganic filler such as carbon and silica. ⁇ 10 alkyl groups.
- the compound represented by the formula (25) is not limited to the following, but examples thereof include 3-chloro-dimethylpropan-1-amine, 3-chloro-diethylpropane-1-amine, and 3-chloro-dibutylpropane.
- the compound represented by the formula (25) is not limited to these compounds, and includes the similar compounds as long as the above conditions are satisfied.
- the compound represented by the formula (25) includes 3-chloro-dibutylpropan-1-amine and 1- (3-chloropropyl) from the viewpoint of reactivity and interaction with inorganic fillers such as carbon and silica. ) Hexamethyleneimine is preferred, and 1- (3-chloropropyl) hexamethyleneimine is more preferred.
- R 14 represents a conjugated diene polymer having a repeating unit represented by any of the following formulas (28) to (30)
- X represents a hydrogen atom.
- the compound represented by the formula (25) is not limited to the following, but examples thereof include N, N-dimethyl-2-butenyl-1-amine, N, N -Diethyl-2-butenyl-1-amine, N, N-dibutyl-2-butenyl-1-amine, N, N-dipropyl-2-butenyl-1-amine, N, N-diheptyl-2-butenyl -1-amine, N, N-dihexyl-2-butenyl-1-amine, N, N-dioctyl-2-butenyl-1-amine, N, N- (di-2-ethylhexyl) -2 -Butenyl-1-amine, N, N-didecyl-2-butenyl-1-amine, N, N-ethylpropyl-2-butenyl-1-amine, N, N-ethylbutyl-2-butenyl-1-amine
- the compound represented by the formula (25) includes N, N-dibutyl from the viewpoint of reducing the hysteresis loss of the modified conjugated diene polymer composition described later.
- Ru-2-butenyl 1-amine, 1- (2-butenyl) piperidine, and 1- (2-butenyl) hexamethyleneimine are preferred, more preferably 1- (2-butenyl) piperidine, and 1- (2- Butenyl) hexamethyleneimine, more preferably 1- (2-butenyl) piperidine.
- the compound represented by the formula (26) is not limited to the following compounds.
- the compound represented by the formula (26) is not limited to these, and includes the similar compounds as long as the above conditions are satisfied.
- the compound represented by the formula (26) is preferably N, N-dimethyl-o-toluidine from the viewpoint of reducing the hysteresis loss of the modified conjugated diene polymer composition described later.
- organic lithium compound examples include, but are not limited to, n-butyllithium, sec-butyllithium, tert-butyllithium, n-propyllithium, and iso-propyllithium.
- the organolithium compound of the present embodiment has at least one nitrogen atom in the molecule from the viewpoints of modification rate improvement and fuel saving performance improvement, and can be used as a polymerization initiator for anionic polymerization. It is preferable to include an organolithium compound represented by any one of the following general formulas (14) to (17).
- R 10 and R 11 are each independently selected from the group consisting of an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 14 carbon atoms, and an aralkyl group having 6 to 20 carbon atoms. At least one selected is shown.
- R 10 and R 11 may be bonded to form a cyclic structure with the adjacent nitrogen atom. In this case, R 10 and R 11 represent an alkyl group having 5 to 12 carbon atoms, It may have a saturated bond or a branched structure.
- R 12 and R 13 are each independently selected from the group consisting of an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 14 carbon atoms, and an aralkyl group having 6 to 20 carbon atoms. At least one selected is shown.
- R 12 and R 13 may be bonded to form a cyclic structure with an adjacent nitrogen atom.
- R 12 and R 13 represent an alkyl group having 5 to 12 carbon atoms, and a part thereof is It may have a saturated bond or a branched structure.
- R 14 represents an alkylene group having 1 to 20 carbon atoms or a conjugated diene polymer having 1 to 20 carbon atoms.
- R 15 and R 16 are each independently selected from the group consisting of an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 14 carbon atoms, and an aryl group having 6 to 20 carbon atoms. At least one selected is shown.
- R 15 and R 16 may be bonded to form a cyclic structure with an adjacent nitrogen atom, in which case R 15 and R 16 represent an alkyl group having 5 to 12 carbon atoms, and branched into a part thereof. You may have a structure.
- R 17 forms a cyclic structure with a nitrogen atom, represents an alkyl group having 2 to 12 carbon atoms in total, and may have an unsaturated bond or a branched structure in a part thereof.
- R 18 represents an alkyl group having 1 to 12 carbon atoms, and a part thereof may have a branched structure.
- R 10 and R 11 represent, for example, methyl group, ethyl group, propyl group, butyl group, octyl group, benzyl group, cyclopropyl group, cyclohexyl group, 3-phenyl-1- A propyl group, an isobutyl group, a decyl group, a heptyl group, and a phenyl group are mentioned.
- R 10 and R 11 are not limited to these, and include analogs thereof as long as the above conditions are satisfied.
- a butyl group and a hexyl group are preferable, and a butyl group is more preferable.
- Examples of the organic lithium compound represented by the formula (14) include, but are not limited to, ethylpropylaminolithium, ethylbutylaminolithium, ethylbenzylaminolithium, dibutylaminolithium, and dihexylaminolithium. Of these, dibutylaminolithium and dihexylaminolithium are preferable, and dibutylaminolithium is more preferable.
- the organolithium compound represented by the formula (14) is not limited to the following.
- the organolithium compound is not limited to these, and includes the similar compounds as long as the above conditions are satisfied.
- piperidinolithium hexamethyleneiminolithium, lithium azacyclooctane, And lithium-1,3,3-trimethyl-6-azabicyclo [3.2.1] octane, more preferably piperidinolithium, hexamethyleneiminolithium, and 3,5-dimethylpiperidinolithium. More preferred is piperidinolithium.
- R 14 represents an alkylene group having 1 to 20 carbon atoms or a conjugated diene polymer having 1 to 20 carbon atoms.
- the conjugated diene polymer preferably represents a conjugated diene polymer having a repeating unit represented by any of the following formulas (18) to (20).
- R 14 when R 14 represents an alkylene group having 1 to 20 carbon atoms, R 14 has 2 to 16 carbon atoms from the viewpoint of reactivity and interaction with inorganic fillers such as carbon and silica. And more preferably an alkylene group having 3 to 10 carbon atoms.
- the organolithium compound represented by the formula (15) is not limited to the following, for example, (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,
- the organolithium compound represented by the formula (15) is Although 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- (Dioctylamino) -2-butenyl) lithium, (4- (di-2-ethylhexylamino) -2-butenyl) lithium, (4- (didecylamino) -2-buteny
- the organolithium compound is not limited to these, and includes the similar compounds as long as the above conditions are satisfied. From the viewpoint of reactivity as an initiator and the viewpoint of chain transfer reaction control described later, 4- (dimethylamino) -2-butenyl) lithium, (4- (diethylamino) -2-butenyl) lithium, and (4- (Dibutylamino) -2-butenyl) lithium is preferred, and (4- (dibutylamino) -2-butenyl) lithium is more preferred.
- the organolithium compound represented by the formula (15) includes (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- (hexamethylene) (Iminyl) ethyl) lithium, (4- (hexamethineleniminyl) butyl) lithium, (5- (hexamethinelenimine) pentyl) lithium, ( -(Hexamethineleniminyl) hexyl) lithium, (10-
- the organolithium compound is not limited to these, and includes the similar compounds as long as the above conditions are satisfied.
- (3- (piperidinyl) propyl) lithium, (3- (hexamethineleniminyl) Propyl) lithium, (3- (1,2,3,6-tetrahydropyridinyl) propyl) lithium, (4- (piperidinyl) -2-butenyl) lithium, (4- (hexamethyleneimine) -Butenyl) lithium is preferred, more preferably (3- (hexamethineleniminyl) propyl) lithium, (4- (piperidinyl) -2-butenyl) lithium, and (4- (hexamethyleneleniminyl) -2 -Butenyl) lithium is preferred, more preferably (4- (piperidinyl) -2-butenyl) lithium.
- the organic lithium compound represented by the formula (16) is not limited to the following, but examples thereof include N, N-dimethyl-o-toluidinolithium, N, N-dimethyl-m-toluidinolithium, N, N-dimethyl-p-toluidinolithium, N, N-diethyl-o-toluidinolithium, N, N-diethyl-m-toluidinolithium, N, N-diethyl-p-toluidinolithium Lithium, N, N-dipropyl-o-toluidinolithium, N, N-dipropyl-m-toluidinolithium, N, N-dipropyl-p-toluidinolithium, N, N-dibutyl-o-to Louisinolithium, N, N-dibutyl-m-toluidinolithium, N, N-dibutyl-p-toluidinolithium, o-piperidinotruenolith
- the organolithium compound represented by the formula (17) is not limited to the following compounds.
- 2- (2-methylpiperidinyl) -1-ethyllithium for example, trade name “AI” manufactured by FMC) -250 ".
- the organolithium compound is not limited to these, and includes the similar compounds as long as the above conditions are satisfied.
- an organolithium compound having at least one nitrogen atom in the molecule Prior to the polymerization step, an organolithium compound having at least one nitrogen atom in the molecule may be prepared in advance, and the method is prepared by any known method.
- the organolithium compound having at least one nitrogen atom in the molecule represented by the formula (14) is obtained by, for example, reacting the compound represented by the formula (24) with the organolithium compound in a hydrocarbon solvent. Obtained by.
- a hydrocarbon solvent an appropriate solvent such as hexane, cyclohexane or benzene may be selected.
- the reaction temperature is preferably 0 ° C. or higher and 80 ° C. or lower, preferably 5.0 ° C. or higher and 70 ° C. or lower, more preferably 7.0 ° C. or higher and 50 ° C. or lower from the viewpoint of productivity.
- the organolithium compound having at least one nitrogen atom in the molecule represented by the formula (15) is, for example, a compound represented by the formula (25) when R 14 represents an alkylene group having 1 to 20 carbon atoms.
- an organic lithium compound are reacted in a hydrocarbon solvent to prepare a lithium amide compound, which is reacted with an alkyl halide represented by the following formula (C), and further reacted with an organic lithium compound. It is done.
- X 1 and X 2 each independently represent an I atom, a Br atom, or a Cl atom
- R 3a represents an alkylene group having 1 to 20 carbon atoms, preferably 2 to 16 represents an alkylene group, more preferably an alkylene group having 3 to 10 carbon atoms.
- the compound represented by the formula (C) is not limited to the following, but examples include 1-bromo-3-chloropropane, 1-bromo-4-chlorobutane, 1-bromo-5-chloropentane, 1-bromo. -6-chlorohexane, 1-bromo-10-chlorodecane, 1-bromo-3-iodopropane, 1-bromo-4-iodobutane, 1-bromo-5-iodopentane, 1-bromo-6-iodohexane, 1 -Bromo-10-iododecane, 1-chloro-3-iodopropane, 1-chloro-4-iodobutane, 1-chloro-5-iodopentane, 1-chloro-6-iodohexane, and 1-chloro-10-iododecane Is mentioned.
- the compound represented by the formula (C) is 1-bromo-3-chloropropane, 1-bromo-4-chlorobutane, 1-bromo-5-chloropentane, 1-bromo-6.
- -Chlorohexane and 1-bromo-10-chlorodecane are preferred, and 1-bromo-3-chloropropane, 1-bromo-4-chlorobutane, and 1-bromo-6-chlorohexane are more preferred.
- the reaction temperature when preparing the lithium amide compound using the compound represented by the formula (25), the organic lithium compound, and the hydrocarbon solvent is as described above.
- the reaction temperature when the compound represented by the formula (C) is reacted with the lithium amide compound is preferably ⁇ 78 ° C. or higher and 70 ° C. or lower, more preferably ⁇ 50 ° C. or higher and 50 ° C. or lower.
- the reaction temperature when the organolithium compound is reacted with the obtained compound is preferably ⁇ 78 ° C. or higher and 70 ° C. or lower, more preferably ⁇ 50 ° C. or higher and 50 ° C. or lower.
- the reaction temperature when preparing the lithium amide compound using the compound represented by the formula (26), the organic lithium compound, and the hydrocarbon solvent is as described above.
- the reaction temperature when the compound represented by the formula (C) is reacted with the lithium amide compound is preferably ⁇ 78 ° C. or higher and 70 ° C. or lower, more preferably ⁇ 50 ° C. or higher and 50 ° C. or lower.
- the reaction temperature when the organolithium compound is reacted with the obtained compound is preferably ⁇ 78 ° C. or higher and 70 ° C. or lower, more preferably ⁇ 50 ° C. or higher and 50 ° C. or lower.
- the organolithium compound having at least one nitrogen atom in the molecule represented by the formula (15) is a conjugated diene heavy compound in which R 14 has a repeating unit represented by any one of the formulas (18) to (20). In the case of indicating coalescence, it is synthesized by the following steps (I) to (IV).
- a compound represented by formula (25) and an organolithium compound are reacted in a hydrocarbon solvent to synthesize a lithium amide compound.
- the obtained lithium amide compound is reacted with butadiene or isoprene in a hydrocarbon solvent.
- Alcohol is added to deactivate lithium and the resulting product is distilled under reduced pressure.
- the product obtained by distillation is reacted with an organolithium compound in a hydrocarbon solvent.
- step (I) in which lithium amide is prepared using the compound represented by formula (25), the organic lithium compound, and the hydrocarbon solvent is as described above.
- general alcohol can be used as the above-mentioned alcohol, those having a low molecular weight are preferable.
- methanol, ethanol, and isopropanol are preferable, and ethanol is more preferable.
- the reaction temperature in step (IV) is preferably 0 ° C. or higher and 80 ° C. or lower, more preferably 10 ° C. or higher and 70 ° C. or lower.
- a polar compound When preparing the organolithium compound, a polar compound may be added to the system. There is a tendency to promote the formation and solubilization in a hydrocarbon solvent.
- the polar compound include, but are not limited to, tertiary monoamines, tertiary diamines, chain ethers, and cyclic ethers.
- the tertiary monoamine is not limited to the following, but for example, trimethylamine, triethylamine, methyldiethylamine, 1,1-dimethoxytrimethylamine, 1,1-diethoxytrimethylamine, 1,1-diethoxytriethylamine, N, N— Examples include dimethylformamide diisopropyl acetal and N, N-dimethylformamide dicyclohexyl acetal.
- the tertiary diamine is not limited to the following, but for example, N, N, N ′, N′-tetramethyldiaminomethane, N, N, N ′, N′-tetramethylethylenediamine, N, N, N ', N'-tetramethylpropanediamine, N, N, N', N'-tetramethyldiaminobutane, N, N, N ', N'-tetramethyldiaminopentane, N, N, N', N'- Examples include tetramethylhexanediamine, dipiperidinopentane, and dipiperidinoethane.
- chain ether examples include, but are not limited to, dimethyl ether, diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, and tetraethylene dimethyl ether.
- cyclic ether examples include, but are not limited to, tetrahydrofuran, bis (2-oxolanyl) ethane, 2,2-bis (2-oxolanyl) propane, 1,1-bis (2-oxolanyl) ethane, 2 2,2-bis (2-oxolanyl) butane, 2,2-bis (5-methyl-2-oxolanyl) propane, and 2,2-bis (3,4,5-trimethyl-2-oxolanyl) propane .
- tertiary monoamines such as trimethylamine and triethylamine
- tertiary diamines such as N, N, N ′, N′-tetramethylethylenediamine
- cyclic ethers such as tetrahydrofuran and 2,2-bis (2-oxolanyl) Propane
- a polar compound may be used individually by 1 type, and may be used in combination of 2 or more type.
- a polar compound when preparing the organolithium compound of the present embodiment, it is preferably added within the range of 30 mass ppm or more and 50000 mass ppm relative to the solvent used when preparing, 200 mass ppm or more It is more preferable to add within the range of 20000 mass ppm or less.
- addition of 30 ppm by mass or more is preferable, ensuring the freedom of microstructure adjustment in the subsequent polymerization step, and the solvent after polymerization.
- the conjugated diene polymer before modification is conjugated using the above-described organolithium compound having at least one nitrogen atom in the molecule, or a polymerization initiator system containing a compound having at least one nitrogen atom and an organolithium compound. It can be obtained by polymerizing using a diene compound or copolymerizing a conjugated diene compound and an aromatic vinyl compound.
- an organolithium compound having at least one nitrogen atom in the molecule is prepared in advance in a predetermined reactor, and polymerization of the conjugated diene compound or copolymerization of the conjugated diene compound and the aromatic vinyl compound is performed.
- the polymerization reaction may be performed by supplying to the reactor to be performed, or the above-described compound having at least one nitrogen atom in the molecule and the organolithium compound may be mixed and prepared using a static mixer or an in-line mixer. .
- the polymerization initiator system may be not only one type but also a mixture of two or more types.
- the conjugated diene polymer before modification is polymerized using a conjugated diene compound or a conjugated diene compound using a polymerization initiator system containing an organic lithium compound and a compound having at least one nitrogen atom in the molecule. And an aromatic vinyl compound.
- the polymerization process of this embodiment may be carried out by either a batch type or a continuous type polymerization method, but from the viewpoint of stably producing a high degree of modification, high molecular weight, and highly branched conjugated diene polymer.
- the polymerization is preferably carried out in a continuous manner, more preferably in a continuous manner in one reactor or two or more connected reactors.
- the polymerization temperature is 45 ° C. or more and 80 ° C. or less
- the solid content is 16.0% by mass or less.
- the concentration of the organolithium compound having at least one nitrogen atom is preferably 0.010 mol / L or less with respect to the volume of the hydrocarbon solvent. Further, in order to make the modification rate 78% by mass or more and MSR 0.45 or less, the polymerization temperature is controlled in the range of 50 ° C. or more and 80 ° C. or less, and the solid content is made 16.0% by mass or less. The concentration of the organolithium compound having at least one nitrogen atom in the molecule is preferably 0.010 mol / L or less with respect to the volume of the hydrocarbon solvent. Furthermore, in order to make the modification rate 80% by mass or more and MSR 0.44 or less, the polymerization temperature is controlled in the range of 50 ° C.
- the concentration of the organolithium compound having at least one nitrogen atom in the molecule is preferably 0.0010 mol / L or less with respect to the volume of the hydrocarbon solvent.
- the polymerization temperature is controlled in the range of 50 ° C. or more and 78 ° C. or less, and the solid content is 16.0% by mass or less.
- numerator shall be 0.0010 mol / L or less with respect to the volume of a hydrocarbon solvent.
- the polymerization temperature is 55 ° C. or more and 76 ° C. or less
- the solid content is 15.0% by mass or less
- the concentration of the organolithium compound having at least one nitrogen atom is preferably 0.0008 mol / L or less with respect to the hydrocarbon solvent.
- achieving a modification rate of 90% by mass or more and an MSR of 0.40 or less that is, achieving a high modification rate, high molecular weight, and high branching.
- a polymerization temperature of 60 ° C. or more and 72 ° C. or less, a solid content of 14.0% by mass or less, and an organic lithium compound having at least one nitrogen atom in the molecule is continuously added;
- the concentration of the compound is 0.00070 mol / L or less with respect to the hydrocarbon solvent.
- the polymerization process of the organolithium compound having at least one nitrogen atom in the molecule may be a continuous type or a batch type. From the viewpoint of production efficiency, a monomer containing a conjugated diene compound and an initiator are placed in a polymerization tank. A continuous system in which the polymer is continuously supplied and continuously polymerized is preferable. In the case of a continuous type, the monomer, solvent and initiator used for polymerization may be fed separately to the polymerization tank, or a method using a mixing tank equipped with a stirrer, a static mixer or a line mixer in the pipe It may be a method of using and continuously mixing.
- the monomer and initiator used for polymerization are preferably diluted with a hydrocarbon solvent.
- a monomer it is preferable that the solid content mentioned later is 16 mass% or less.
- the concentration of the organolithium compound having at least one nitrogen atom in the molecule is 0.010 mol / L or less with respect to the hydrocarbon solvent. It is preferably 0.0010 mol / L or less, more preferably 0.0008 mol / L or less, and the lower limit is not particularly limited, but is preferably 0.000001 mol / L or more.
- the polymerization method is continuous, and the concentration of the organolithium compound having at least one nitrogen atom in the molecule is 0. 0 relative to the volume of the hydrocarbon solvent. It is preferably 010 mol / L or less, more preferably 0.0010 mol / L or less, even more preferably 0.0008 mol / L or less, and the lower limit is not particularly limited, but is 0.000001 mol / L or more. Preferably there is.
- the conjugated diene polymer becomes a copolymer of a conjugated diene compound and an aromatic vinyl compound by using a polymerization initiator system containing a compound having at least one nitrogen atom in the molecule and an organolithium compound in the present embodiment.
- a polymerization initiator system containing a compound having at least one nitrogen atom in the molecule and an organolithium compound in the present embodiment.
- the chain transfer reaction is promoted by the influence of at least one nitrogen atom in the molecule of the polymerization initiator system, so that the living terminal active terminal is lost.
- specific manufacturing conditions tend to be required.
- the chain transfer rate or the chain transfer rate is increased, the number average molecular weight of the obtained polymer is decreased, the degree of branching is increased, the molecular weight distribution is widened, and the aromatics are increased. Since the block portion in which 30 or more vinyl units are linked tends to decrease or disappear, MSR tends to decrease. However, it is presumed that the inactivation of the living active terminal is promoted, and if the production conditions are not controlled, the modification rate tends to decrease. Note that, in each of the batch type polymerization method and the continuous type polymerization method, the continuous polymerization method tends to advance the chain transfer reaction.
- the polymerization temperature is not particularly limited as long as the anionic polymerization proceeds, the chain transfer reaction is controlled, and the number of blocks in which the aromatic vinyl compound units are linked is 30 or more, but it is not particularly limited. From the viewpoint of controlling the chain transfer reaction and ensuring a sufficient reaction amount of the modifier with respect to the active terminal after completion of the polymerization, it is more preferably 80 ° C. or less. From the viewpoint that the number of blocks in which 30 or more vinyl units are linked is small, 50 ° C. or higher and 78 ° C. or lower is more preferable, and 60 ° C. or higher and 75 ° C. or lower is even more preferable.
- the solid is a content of the conjugated diene compound and the aromatic vinyl compound, and the total mass of the solvent, such as the conjugated diene compound and the aromatic vinyl compound.
- the content also referred to as “monomer concentration” is preferably 16% by mass or less, more preferably 15% by mass or less, and still more preferably 14% by mass or less.
- the lower limit of the solid content is not particularly limited, but is preferably 5.0% by mass or more.
- the polymerization method is continuous, the polymerization temperature is 45 ° C. or higher and 80 ° C. or lower, and the solid content is 16% by mass or less. Is preferred.
- the conjugated diene polymer of this embodiment is obtained by polymerizing at least a conjugated diene compound in a hydrocarbon solvent, and may be obtained by copolymerizing a conjugated diene compound and an aromatic vinyl compound.
- the conjugated diene polymer is preferably obtained by growing by an anionic polymerization reaction using a continuous polymerization method using an organolithium compound having at least one nitrogen atom in the molecule as a polymerization initiator.
- the conjugated diene polymer is more preferably a polymer having an active end obtained by a growth reaction by living anion polymerization. Thereby, a modified conjugated diene polymer having a high modification rate can be obtained.
- the conjugated diene compound is not limited to the following as long as it is a polymerizable monomer.
- 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene , 3-methyl-1,3-pentadiene, 1,3-heptadiene, and 1,3-hexadiene are preferable from the viewpoint of industrial availability. These may be used alone or in combination of two or more.
- the aromatic vinyl compound is not limited to the following as long as it is a monomer copolymerizable with a conjugated diene compound.
- styrene, p-methylstyrene, ⁇ -methylstyrene, vinylethylbenzene, vinylxylene, vinyl Naphthalene and diphenylethylene are mentioned.
- styrene is preferable from the viewpoint of industrial availability. These may be used alone or in combination of two or more.
- the polymerization step is preferably performed in a solvent.
- the solvent include hydrocarbon solvents such as saturated hydrocarbons and aromatic hydrocarbons.
- Specific hydrocarbon solvents include, but are not limited to, aliphatic hydrocarbons such as butane, pentane, hexane, and heptane; alicyclic carbons such as cyclopentane, cyclohexane, methylcyclopentane, and methylcyclohexane.
- Hydrogen Hydrocarbons composed of aromatic hydrocarbons such as benzene, toluene and xylene and mixtures thereof.
- the conjugated diene compound, the aromatic vinyl compound, and the polymerization solvent are each treated alone or mixed with these mixed solutions in advance before being subjected to a polymerization reaction by reacting the organometallic compound with allenes and acetylenes that are impurities. You can also keep it. Thereby, inhibition of polymerization by impurities can be prevented, the active terminal amount of the polymer becomes high, a sharper molecular weight distribution (Mw / Mn) can be achieved, and a higher modification rate tends to be achieved. ,preferable.
- a polar compound may be added.
- An aromatic vinyl compound can be randomly copolymerized with a conjugated diene compound and tends to be used as a vinylating agent for controlling the microstructure of the conjugated diene portion. It is also effective in improving the polymerization rate.
- polar compounds include, but are not limited to, tetrahydrofuran, diethyl ether, dioxane, ethylene glycol dimethyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol dibutyl ether, dimethoxybenzene, 2,2-bis (2-oxolanyl).
- Ethers such as propane; Tertiary amine compounds such as tetramethylethylenediamine, dipiperidinoethane, trimethylamine, triethylamine, pyridine, quinuclidine; potassium tert-amylate, potassium tertbutylate, sodium tertbutylate, Examples include alkali metal alkoxide compounds such as sodium amylate; and phosphine compounds such as triphenylphosphine. These polar compounds may be used alone or in combination of two or more.
- the amount of the polar compound used is not particularly limited and can be selected according to the purpose, but is preferably 0.01 mol or more and 100 mol or less with respect to 1 mol of the polymerization initiator.
- An appropriate amount of such a polar compound (vinylating agent) can be used as a regulator of the microstructure of the polymer conjugated diene moiety depending on the desired vinyl bond amount.
- Many polar compounds simultaneously have an effective randomizing effect in the copolymerization of conjugated diene compounds and aromatic vinyl compounds, and tend to be used to adjust the distribution of aromatic vinyl compounds and adjust the amount of styrene block It is in.
- a part of 1,3-butadiene is intermittently interrupted during the copolymerization.
- a method of adding them may be used.
- the amount of the conjugated diene in the conjugated diene polymer of the present embodiment is not particularly limited, but is preferably 50% by mass or more and 100% by mass or less, and more preferably 60% by mass or more and 80% by mass or less. .
- the amount of bonded aromatic vinyl in the conjugated diene polymer of the present embodiment is not particularly limited, but is preferably 0% by mass to 50% by mass, and more preferably 20% by mass to 40% by mass. Is more preferable. If the amount of bound conjugated diene and amount of bound aromatic vinyl are in the above ranges, a vulcanizate that has a better balance between low hysteresis loss and wet skid resistance, and that is more satisfactory in wear resistance and fracture strength can be obtained. It tends to be possible.
- the amount of bonded aromatic vinyl can be measured by ultraviolet absorption of a phenyl group, and the amount of bonded conjugated diene can also be obtained from this. Specifically, it measures according to the method as described in the Example mentioned later.
- the vinyl bond amount in the conjugated diene bond unit is not particularly limited, but is preferably 10 mol% or more and 75 mol% or less, and more preferably 25 mol% or more and 65 mol% or less.
- a vulcanizate having a further excellent balance between low hysteresis loss and wet skid resistance and more satisfactory wear resistance and fracture strength tends to be obtained.
- the modified conjugated diene polymer is a copolymer of butadiene and styrene
- in the butadiene bond unit by the method of Hampton (RR Hampton, Analytical Chemistry, 21, 923 (1949)).
- the vinyl bond amount (1,2-bond amount) can be determined. Specifically, it is measured by the method described in the examples described later.
- the conjugated diene polymer may be a random copolymer or a block copolymer.
- the random copolymer include, but are not limited to, for example, butadiene-isoprene random copolymer, butadiene-styrene random copolymer, isoprene-styrene random copolymer, butadiene-isoprene-styrene random copolymer. Is mentioned.
- the composition distribution of each monomer in the copolymer chain is not particularly limited. For example, a completely random copolymer close to a statistical random composition, a taper (gradient) random in which the composition is distributed in a tapered shape. A copolymer is mentioned.
- the bonding mode of the conjugated diene that is, the composition of 1,4-bonds, 1,2-bonds, etc. may be uniform or distributed.
- the block copolymer is not limited to the following, for example, a 2-type block copolymer consisting of 2 blocks, a 3-type block copolymer consisting of 3 blocks, and a 4-type block copolymer consisting of 4 blocks. Coalescence is mentioned.
- a block composed of an aromatic vinyl compound such as styrene is represented by S
- S an aromatic vinyl compound
- B conjugated diene compound
- B a block composed of a copolymer of an aromatic vinyl compound and a conjugated diene compound
- S—B2 type block copolymer an S—B—S3 type block copolymer
- S—B—S—B4 type block copolymer and the like.
- each block need not be clearly distinguished.
- the aromatic vinyl compound in the block B may be distributed uniformly or in a tapered shape.
- a plurality of portions where the aromatic vinyl compound is uniformly distributed and / or portions where the aromatic vinyl compound is distributed in a tapered shape may coexist in the block B.
- a plurality of segments having different aromatic vinyl compound contents may coexist in the block B.
- the conjugated diene polymer obtained by the above-described production method can be further hydrogenated in an inert solvent to convert all or part of the double bonds to saturated hydrocarbons. it can. In that case, heat resistance and weather resistance are improved, and the product tends to be prevented from being deteriorated when processed at a high temperature. As a result, it exhibits even better performance in various applications such as automotive applications.
- the hydrogenation rate of the unsaturated double bond based on the conjugated diene compound can be arbitrarily selected according to the purpose and is not particularly limited. When used as a vulcanized rubber, it is preferable that the double bond of the conjugated diene part partially remains. From this viewpoint, the hydrogenation rate of the conjugated diene part in the polymer is preferably 3.0% or more and 70% or less, more preferably 5.0% or more and 65% or less, and more preferably 10% or more and 60%. More preferably, it is as follows.
- the hydrogenation rate of the aromatic double bond based on the aromatic vinyl compound in the copolymer of the conjugated diene compound and the aromatic vinyl compound is not particularly limited, but is preferably 50% or less, 30 % Or less is more preferable, and 20% or less is further preferable.
- the hydrogenation rate can be determined by a nuclear magnetic resonance apparatus (NMR).
- the hydrogenation method is not particularly limited, and a known method can be used.
- a suitable hydrogenation method includes a method of hydrogenating by blowing gaseous hydrogen into the polymer solution in the presence of a catalyst.
- a catalyst for example, a heterogeneous catalyst such as a catalyst in which a noble metal is supported on a porous inorganic substance; a catalyst in which a salt such as nickel or cobalt is solubilized and reacted with organic aluminum or the like, or a metallocene such as titanocene is used. Examples thereof include homogeneous catalysts such as catalysts. Among these, a titanocene catalyst is preferable from the viewpoint of selecting mild hydrogenation conditions.
- the hydrogenation of the aromatic group can be performed by using a noble metal supported catalyst.
- the hydrogenation catalyst are not limited to the following.
- hydrogenation catalysts for example, JP-B-42-8704, JP-B-43-6636, JP-B-63-4841, JP-B-1-37970, JP-B-1-53851, Examples thereof also include hydrogenation catalysts described in Japanese Patent Publication No. 2-9041 and Japanese Patent Application Laid-Open No. 8-109219.
- a preferable hydrogenation catalyst includes a reaction mixture of a titanocene compound and a reducing organometallic compound.
- the total content concentration (mass) of these impurities is preferably 200 ppm by mass or less, more preferably 100 ppm by mass or less, and 50 ppm by mass or less based on the total amount of the conjugated diene compound. More preferably.
- allenes include propadiene and 1,2-butadiene.
- acetylenes include ethyl acetylene and vinyl acetylene.
- the DSC curve is recorded while raising the temperature in a predetermined temperature range, and the peak top (Inflection point) of the DSC differential curve is set as the glass transition temperature. Specifically, it is measured by the method described in the examples described later.
- the conjugated diene polymer of the present embodiment is a copolymer of a conjugated diene compound and an aromatic vinyl compound
- the number of blocks in which 30 or more aromatic vinyl units are linked is small or absent. Is preferred.
- the copolymer is a butadiene-styrene copolymer
- the method described in Kolthoff method described in IM KOLTHOFF, et al., J. Polym. Sci. 1, 429 (1946)).
- a block in which 30 or more aromatic vinyl units are chained is preferably 5.0% by mass or less based on the total amount of the polymer, More preferably, it is 3.0 mass% or less.
- a conjugated diene polymer is modified with a modifier having four or more alkoxy groups bonded to a silyl group and a tertiary amino group in one molecule. It has a denaturation step.
- ⁇ Modifier> As the modifier of this embodiment, in order to obtain a modified conjugated diene polymer having an MSR of 0.45 or less and a modification rate of 75% by mass or more, the activity in the conjugated diene polymer derived from the polymerization initiator By reacting with the terminal, at least one functional group selected from the group consisting of a multi-branched structure having three or more branches and an alkoxy group, a halogen group, and an amino group bonded to a silicon atom by the modification step, A modifier that can be introduced into the polymer is preferred.
- Examples of the functional group of the modifier that reacts with the active terminal in the conjugated diene polymer derived from the polymerization initiator include an alkoxysilyl group, a silazane group, and a halosilyl group.
- the number of branches of the multi-branched structure can be adjusted by the number of functional groups in the modifier and the addition rate of the modifier, and the number of branches is preferably 3 or more, more preferably 4 or more.
- As the functional group that can be introduced into the conjugated diene polymer by the modification step an alkoxy group bonded to a silicon atom and an amino group are more preferable.
- modifying agent examples include 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-silacycloheptanthris (3-trimethoxysilylpropyl) amine, tris (3-methyldimethoxysilylpropyl) amine, tris (3- And tris (3-methyldiethoxysilylpropyl) amine.
- the modifier preferably contains a modifier represented by any of the following general formulas (1) to (3).
- R 1 to R 4 each independently represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms
- R 5 represents an alkylene group having 1 to 10 carbon atoms
- R 6 represents an alkylene group having 1 to 20 carbon atoms.
- m represents an integer of 1 or 2
- n represents an integer of 2 or 3
- (m + n) represents an integer of 4 or more.
- R 1 to R 6 each independently represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms
- R 7 to R 9 each independently represents An alkylene group having 1 to 20 carbon atoms is shown.
- m, n, and l each independently represent an integer of 1 to 3, and (m + n + 1) represents an integer of 4 or more.
- R 1 to R 4 each independently represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms
- R 5 and R 6 are each independently An alkylene group having 1 to 20 carbon atoms
- m and n each independently represents an integer of 1 to 3
- (m + n) represents an integer of 4 or more
- R 7 represents an integer of 1 to 3 carbon atoms.
- the modifying agent represented by the formula (1) is not limited to the following, but for example, 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) -1-aza -2-Silacyclopentane, 2,2-diethoxy-1- (3-diethoxyethylsilylpropyl) -1-aza-2-silacyclopentane, 2-methoxy, 2-methyl 1- (3-trimeth
- m is 2 and n is 3 are preferable from the viewpoints of reactivity and interaction between the functional group of the modifier and an inorganic filler such as silica, and processability.
- an inorganic filler such as silica
- 2,2-dimethoxy-1- (3-trimethoxysilylpropyl) -1-aza-2-silacyclopentane and 2,2-diethoxy-1- (3-triethoxysilylpropyl)- 1-aza-2-silacyclopentane is preferred.
- reaction temperature, reaction time, and the like when the modifier represented by formula (1) is reacted with the polymerization active terminal there are no particular limitations on the reaction temperature, reaction time, and the like when the modifier represented by formula (1) is reacted with the polymerization active terminal, but the reaction may be performed at 0 ° C. or higher and 120 ° C. or lower for 30 seconds or longer. preferable.
- the total number of moles of the alkoxy group bonded to the silyl group in the compound of the modifier represented by the formula (1) is 0.6 of the number of moles of addition of the alkali metal compound and / or alkaline earth metal compound of the polymerization initiator.
- the resulting modified conjugated diene polymer is preferably 0.6 times or more, and the polymer ends are coupled to each other for improved processability.
- it is preferably 3.0 times or less from the viewpoint of the modifier cost.
- the modifying agent represented by the formula (2) is not limited to the following, but for example, tris (3-trimethoxysilylpropyl) amine, tris (3-methyldimethoxysilylpropyl) amine, tris (3-tri Ethoxysilylpropyl) amine, tris (3-methyldiethoxysilylpropyl) amine, tris (trimethoxysilylmethyl) amine, tris (2-trimethoxysilylethyl) amine, and tris (4-trimethoxysilylbutyl) amine Can be mentioned.
- n, m, and l all represent 3. preferable.
- Preferable specific examples include tris (3-trimethoxysilylpropyl) amine and tris (3-triethoxysilylpropyl) amine.
- reaction temperature, reaction time, etc. when the modifier represented by formula (2) is reacted with the polymerization active terminal, but the reaction may be carried out at 0 ° C. or higher and 120 ° C. or lower for 30 seconds or longer. preferable.
- the total number of moles of alkoxy groups bonded to the silyl group in the compound of the modifier represented by formula (2) is 0.6 times or more and 3.0 times the number of moles of lithium constituting the polymerization initiator system described above.
- the range is preferably in the range of 0.8 times or more and 2.5 times or less, more preferably in the range of 0.8 times or more and 2.0 times or less.
- the modified conjugated diene polymer From the viewpoint of obtaining a sufficient modification rate and molecular weight and branched structure in the modified conjugated diene polymer, it is preferably 0.6 times or more, and the polymer ends are coupled to improve the workability. In addition to obtaining the coalescing component, it is preferably 3.0 times or less from the viewpoint of the modifier cost.
- the modifier represented by the formula (3) is not limited to the following, but examples thereof include bis (3- (methylamino) propyl) trimethoxysilane and bis (3- (ethylamino) propyl) trimethoxysilane. Bis (3- (propylamino) propyl) trimethoxysilane, and bis (3- (butylamino) propyl) trimethoxysilane.
- n, m, and l are all represented by 3 from the viewpoint of reactivity and interaction between the functional group of the modifier and an inorganic filler such as silica, and from the viewpoint of processability. preferable.
- Preferable specific examples include bis (3- (methylamino) propyl) trimethoxysilane and bis (3- (ethylamino) propyl) trimethoxysilane.
- reaction temperature There are no particular limitations on the reaction temperature, reaction time, and the like when the modifier represented by formula (3) is reacted with the polymerization active terminal, but the reaction may be performed at 0 ° C. or higher and 120 ° C. or lower for 30 seconds or longer. preferable.
- the modifier is a viewpoint of obtaining a modified conjugated diene polymer having an excellent balance between high modification rate, high molecular weight, and high branching, and fuel saving performance when processed into a vulcanizate, workability, and wear resistance.
- m in the formula (1) represents 2 and n represents 3, or the formula (2) contains a modifier, and the formula In (2), m, n, and l are all preferably 3 and are preferably modifying agents.
- the total number of moles of alkoxy groups bonded to the silyl group in the compound of the modifier represented by the formula (3) is 0.6, which is the number of moles of the alkali metal compound and / or alkaline earth metal compound added as the polymerization initiator. It is preferably a range that is not less than twice and not more than 3.0 times, more preferably in a range that is not less than 0.8 times and not more than 2.5 times, and in a range that is not less than 0.8 times and not more than 2.0 times More preferably it is. From the viewpoint of obtaining a sufficient modification rate and molecular weight and branched structure, the resulting modified conjugated diene polymer is preferably 0.6 times or more, and the polymer ends are coupled to each other for improved processability. In addition to preferably obtaining the polymer component, it is preferably 3.0 times or less from the viewpoint of the modifier cost.
- the content of the conjugated diene compound is preferably 100 mass ppm or more and 50000 mass ppm or less, and 200 mass ppm or more with respect to the total amount of the monomer and the polymer. It is more preferably 10,000 ppm by mass or less, and further preferably 300 ppm by mass or more and 5000 ppm or less.
- the content of the monomer containing the conjugated diene compound in the solution can be measured by the method described in the examples described later.
- a deactivation agent, a neutralizing agent, and the like may be added to the copolymer solution after the modification reaction, if necessary.
- the quenching agent include, but are not limited to, water; alcohols such as methanol, ethanol, and isopropanol.
- the neutralizing agent include, but are not limited to, carboxylic acids such as stearic acid, oleic acid, and versatic acid; aqueous solutions of inorganic acids, and carbon dioxide.
- a stabilizer for rubber from the viewpoint of preventing gel formation after polymerization and improving the stability during processing.
- the rubber stabilizer is not limited to the following, and known ones can be used.
- BHT 2,6-di-tert-butyl-4-hydroxytoluene
- n-octadecyl-3 Antioxidants such as — (4′-hydroxy-3 ′, 5′-di-tert-butylphenol) propinate and 2-methyl-4,6-bis [(octylthio) methyl] phenol are preferred.
- an extension oil can be added to the modified conjugated diene copolymer as necessary.
- the method of adding the extender oil to the modified conjugated diene polymer is not limited to the following, but the extender oil is added to the polymer solution and mixed to remove the solvent from the oil-extended copolymer solution.
- the method is preferred.
- the extending oil include aroma oil, naphthenic oil, and paraffin oil.
- an aromatic substitute oil having a polycyclic aromatic (PCA) component of 3% by mass or less by the IP346 method is preferable.
- aroma substitute oils examples include TDAE (Treated Displaced Aromatic Extracts), MES (Middle Extraction Solt), and MES (Middle Extraction Soltrate) as shown in Kautschuk Kunststoffe 52 (12) 799 (1999).
- TDAE Teated Displaced Aromatic Extracts
- MES Middle Extraction Solt
- MES Middle Extraction Soltrate
- the addition amount of extending oil is not specifically limited, 10 mass parts or more and 60 mass parts are preferable with respect to 100 mass parts of modified conjugated diene polymers, and 15 mass parts or more and 37.5 mass parts or less are more preferable.
- the method for producing a modified conjugated diene polymer of the present embodiment can further include a solvent removal step.
- the solvent removal step is a step of obtaining the modified conjugated diene polymer from the polymer solution, and a known method can be used.
- the method for example, after separating the solvent by steam stripping or the like, the polymer is filtered and further dehydrated and dried to obtain the polymer, concentrated in a flushing tank, and further a vent extruder, etc. And a method of directly devolatilizing with a drum dryer or the like.
- the modified conjugated diene polymer of this embodiment is suitably used as a vulcanizate.
- the vulcanized product may be, for example, a modified conjugated diene polymer of the present embodiment, if necessary, an inorganic filler such as a silica-based inorganic filler or carbon black, or a modified conjugated diene polymer of the present embodiment.
- an inorganic filler such as a silica-based inorganic filler or carbon black
- a modified conjugated diene polymer of the present embodiment Mix with rubbery polymer, silane coupling agent, rubber softener, wax, vulcanizing agent, vulcanization accelerator, vulcanization aid, etc. to make a modified conjugated diene polymer composition, then heat.
- a modified conjugated diene comprising a rubber component and 0.5 to 300 parts by mass of a silica-based inorganic filler with respect to 100 parts by mass of the rubber component.
- a polymer composition is preferred.
- the rubber component is more preferably a modified conjugated diene polymer composition containing 20 parts by mass or more of the modified conjugated diene polymer of the present embodiment with respect to 100 parts by mass of the rubber component.
- a rubbery polymer other than the modified conjugated diene polymer of this embodiment can be used in combination with the modified conjugated diene polymer of this embodiment.
- examples of such rubbery polymers include, but are not limited to, for example, conjugated diene polymers or hydrogenated products thereof, random copolymers of conjugated diene compounds and vinyl aromatic compounds, or hydrogenated products thereof. Products, block copolymers of conjugated diene compounds and vinyl aromatic compounds or hydrogenated products thereof, non-diene polymers, and natural rubber.
- More specific rubbery polymers include, for example, butadiene rubber or hydrogenated product thereof, isoprene rubber or hydrogenated product thereof, styrene-butadiene rubber or hydrogenated product thereof, styrene-butadiene block copolymer or hydrogenated product thereof.
- styrene elastomer such as styrene-isoprene block copolymer or hydrogenated product thereof, acrylonitrile-butadiene rubber or hydrogenated product thereof.
- the rubbery polymer of the non-diene polymer is not limited to the following, but for example, ethylene-propylene rubber, ethylene-propylene-diene rubber, ethylene-butene-diene rubber, ethylene-butene rubber, ethylene-hexene rubber, ethylene- Olefin-based elastomers such as octene rubber; butyl rubber, brominated butyl rubber, acrylic rubber, fluorine rubber, silicone rubber, chlorinated polyethylene rubber, epichlorohydrin rubber, ⁇ , ⁇ -unsaturated nitrile-acrylic ester-conjugated diene copolymer rubber, urethane rubber , And polysulfide rubber.
- the various rubber-like polymers described above may be modified rubbers to which functional groups having polarity such as hydroxyl groups and amino groups are added.
- the weight average molecular weight is preferably 2000 or more and 200000 or less, and more preferably 5000 or more and 1500,000 or less, from the viewpoint of a balance between performance and processing characteristics.
- the weight average molecular weight can be measured by the same method as the method for measuring the modified conjugated diene polymer described in the Examples.
- a so-called liquid rubber having a low molecular weight can also be used as the rubbery polymer.
- These rubbery polymers may be used alone or in combination of two or more.
- the blending ratio (mass ratio) thereof is (modified conjugated diene polymer weight). 20/80 or more and 100/0 or less is preferable, 30/70 or more and 90/10 or less is more preferable, and 50/50 or more and 80/20 or less is more preferable.
- the (modified conjugated diene polymer / rubber-like polymer) is within the above range, a vulcanizate having a better balance between low hysteresis loss and wet skid resistance and further satisfying wear resistance and fracture strength. Tend to be able to get.
- the modified conjugated diene polymer composition includes 100 parts by mass of a rubber component containing 20 parts by mass or more of the modified conjugated diene polymer described above, and 0.5 to 300 parts by mass of a silica-based inorganic filler. Those are more preferred. Dispersing the silica-based inorganic filler in the modified conjugated diene polymer of the present embodiment provides an excellent balance between low hysteresis loss and wet skid resistance when used as a vulcanizate, and is practically sufficient It has a high wear resistance and fracture strength, and tends to be able to impart excellent workability when used as a vulcanizate. Even when the modified conjugated diene polymer composition of the present embodiment is used for vulcanized rubber applications such as tires, automobile parts such as vibration-proof rubber, and shoes, it is preferable that a silica-based inorganic filler is included.
- the silica-based inorganic filler is not particularly limited, but may be a known, solid particles preferably comprise SiO 2 or Si 3 Al as a constituent unit, the main structural units of SiO 2 or Si 3 Al More preferably, it is a component.
- a main component means the component contained in a silica type inorganic filler 50 mass% or more, Preferably it is 70 mass% or more, More preferably, it is 80 mass% or more.
- silica-based inorganic filler examples include, but are not limited to, inorganic inorganic substances such as silica, clay, talc, mica, diatomaceous earth, wollastonite, montmorillonite, zeolite, and glass fiber.
- inorganic inorganic substances such as silica, clay, talc, mica, diatomaceous earth, wollastonite, montmorillonite, zeolite, and glass fiber.
- trade name “Ultrasil 7000GR” manufactured by Evonik Degussa may be mentioned.
- the mixture of the silica type inorganic filler which hydrophobized the surface, and a silica type inorganic filler and inorganic fillers other than a silica type is also mentioned.
- silica and glass fiber are preferable from the viewpoint of strength and wear resistance, and silica is more preferable.
- examples of silica include dry silica, wet silica, and synthetic silicate silica.
- wet silica is more preferable from the viewpoint of excellent balance between the fracture property improvement effect and wet skid resistance.
- the nitrogen adsorption specific surface area required by the BET adsorption method of the silica-based inorganic filler is 100 m 2 / g or more and 300 m 2.
- the specific surface area is relatively small (for example, a silica-based inorganic filler having a specific surface area of 200 m 2 / g or less), and the specific surface area is relatively large (for example, silica having a specific surface area of 200 m 2 / g or more).
- System inorganic fillers can be used in combination. Thereby, it is possible to highly balance good wear resistance and fracture characteristics with low hysteresis loss.
- the compounding amount of the silica-based inorganic filler in the modified conjugated diene polymer composition is 0.5 parts by mass or more with respect to 100 parts by mass of the rubber component containing the modified conjugated diene polymer of the present embodiment. It is preferably 300 parts by mass or less, more preferably 5.0 parts by mass or more and 200 parts by mass or less, and further preferably 20 parts by mass or more and 100 parts by mass or less.
- the compounding amount of the silica-based inorganic filler is preferably 0.5 parts by mass or more from the viewpoint of manifesting the effect of adding the inorganic filler.
- the inorganic filler is sufficiently dispersed to process the composition. And from the viewpoint of making the mechanical strength practically sufficient, it is preferably 300 parts by mass or less.
- the modified conjugated diene polymer composition may further contain carbon black.
- the carbon black is not limited to the following, and examples thereof include carbon blacks of each class such as SRF, FEF, HAF, ISAF, and SAF.
- SRF sulfur adsorption specific surface area
- FEF fluorescence-activated fluoride
- HAF high-density polyethylene
- ISAF ISAF
- SAF sulfur adsorption-sensitive adsorption specific surface area of 50 m 2 / g or more and a dibutyl phthalate (DBP) oil absorption of 80 mL / 100 g or less is preferable.
- DBP dibutyl phthalate
- the blending amount of carbon black is preferably 0.5 parts by mass or more and 100 parts by mass or less, and 3.0 parts by mass or more and 100 parts by mass or less with respect to 100 parts by mass of the rubber component containing the modified conjugated diene polymer of the present embodiment. Is more preferable, and 5.0 mass parts or more and 50 mass parts or less are still more preferable.
- the blending amount of carbon black is preferably 0.5 parts by mass or more from the viewpoint of expressing the performance required for applications such as dry grip performance and conductivity, and from the viewpoint of dispersibility, 100 parts by mass. The following is preferable.
- the modified conjugated diene polymer composition may further contain a metal oxide or a metal hydroxide in addition to the silica inorganic filler or carbon black.
- Metal oxide refers to solid particles having the chemical formula MxOy (M represents a metal atom, and x and y each independently represents an integer of 1 to 6) as a main component of a structural unit, for example, Alumina, titanium oxide, magnesium oxide, and zinc oxide can be used. A mixture of a metal oxide and an inorganic filler other than the metal oxide can also be used.
- the metal hydroxide include, but are not limited to, aluminum hydroxide, magnesium hydroxide, and zirconium hydroxide.
- the modified conjugated diene polymer composition may further contain a silane coupling agent.
- the silane coupling agent has a function to close the interaction between the rubber component and the silica-based inorganic filler, and has an affinity or binding group for each of the rubber component and the silica-based inorganic filler.
- a compound having a sulfur bond portion, an alkoxysilyl group, and a silanol group portion in one molecule is used.
- examples of the commercially available product include a trade name “Si75” manufactured by Evonik Degussa.
- the blending amount 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, with respect to 100 parts by mass of the silica-based inorganic filler described above. 1.0 mass part or more and 15 mass parts or less are more preferable. When the blending amount of the silane coupling agent is within the above range, the addition effect of the silane coupling agent tends to be more remarkable.
- the modified conjugated diene polymer composition may further contain a rubber softener.
- a rubber softener mineral oil or a liquid or low molecular weight synthetic softener is suitable.
- the mineral oil rubber softener called process oil or extender oil used for softening, increasing volume and improving processability of rubber is a mixture of aromatic ring, naphthene ring and paraffin chain.
- a paraffin chain having 50% or more carbon atoms in the total carbon is called a paraffin type, a naphthene ring carbon number of 30% or more and 45% or less is a naphthene type, and an aromatic carbon number exceeds 30%. It is called aromatic.
- the blending amount of the rubber softener is preferably 0 to 100 parts by weight, preferably 10 to 90 parts by weight, with respect to 100 parts by weight of the rubber component containing the modified conjugated diene polymer of the present embodiment. Is more preferable, and 30 mass parts or more and 90 mass parts or less are still more preferable. When the blending amount of the rubber softener is 100 parts by mass or less with respect to 100 parts by mass of the rubber component, bleeding out and stickiness of the composition surface tend to be suppressed.
- silica-based inorganic fillers silica-based inorganic fillers, carbon black and other fillers, silane coupling agents, rubber softeners and the like.
- the method for example, an open roll, a Banbury mixer, a kneader, a single screw extruder, a twin screw extruder, a melt screw kneading method using a general mixer such as a multi screw extruder, etc., each component is dissolved and mixed Thereafter, there is a method of removing the solvent by heating.
- melt kneading method using a roll, a Banbury mixer, a kneader, and an extruder is preferable from the viewpoints of productivity and good kneading properties.
- any of a method of kneading the modified conjugated diene polymer and various compounding agents at a time and a method of mixing in multiple times can be applied.
- the modified conjugated diene polymer composition may be a vulcanized composition that has been vulcanized with a vulcanizing agent.
- a vulcanizing agent 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, polymeric polysulfur compounds, and the like.
- the amount of the vulcanizing agent used is preferably 0.01 parts by mass or more and 20 parts by mass or less, and 0.1 parts by mass or more and 15 parts by mass with respect to 100 parts by mass of the rubber component containing the modified conjugated diene polymer of the present embodiment.
- the vulcanization method a conventionally known method can be applied, and the vulcanization temperature is preferably 120 ° C. or higher and 200 ° C. or lower, more preferably 140 ° C. or higher and 180 ° C. or lower.
- a vulcanization accelerator and a vulcanization aid may be used as necessary.
- the vulcanization accelerator conventionally known materials can be used. For example, sulfenamide, guanidine, thiuram, aldehyde-amine, aldehyde-ammonia, thiazole, thiourea, dithiocarbamate And the like. Specific examples of the compound include N-cyclohexyl-2-benzothiazylsulfinamide and diphenylguanidine.
- cure adjuvant although not limited to the following, For example, zinc white and a stearic acid are mentioned.
- the amount of the vulcanization accelerator used is preferably 0.01 parts by mass or more and 20 parts by mass or less, and 0.1 parts by mass or more with respect to 100 parts by mass of the rubber component containing the modified conjugated diene polymer of the present embodiment. 15 parts by mass or less is more preferable.
- the modified conjugated diene-based polymer composition includes other softeners and fillers other than those described above within the range that does not impair the object of the present embodiment, and the trade name “Sannok N” manufactured by Ouchi Shinsei Chemical Co., Ltd.
- Various additives such as waxes, heat resistance stabilizers, antistatic agents, weather resistance stabilizers, anti-aging agents such as N-isopropyl-N′-phenyl-p-phenylenediamine, colorants, lubricants and the like may be used.
- known softeners can be used.
- examples of other fillers include calcium carbonate, magnesium carbonate, aluminum sulfate, and barium sulfate.
- Known materials can be used as the above heat stabilizer, antistatic agent, weathering stabilizer, anti-aging agent, colorant, and lubricant.
- the rotor was rotated at 2 rpm, and the torque after 4 minutes was measured to obtain the Mooney viscosity (ML (1 + 4)). Thereafter, when the modified conjugated diene polymer was used as a sample, the rotation of the rotor was immediately stopped, and the torque every 0.1 second for 1.6 to 5 seconds after recording was recorded in Mooney units. The slope of the straight line when the time (seconds) was log-log plotted was determined, and the absolute value thereof was taken as the Mooney relaxation rate (MSR).
- MSR Mooney relaxation rate
- Sample preparation 10 mg of sample and 5 mg of standard polystyrene were dissolved in 20 mL of tetrahydrofuran (THF).
- THF tetrahydrofuran
- the column used was a guard column: trade name “TSKguardcolumn HHR-H” manufactured by Tosoh Corporation and a column: 3 trade names “TSKgel SuperMultipore HZ-H” manufactured by Tosoh Corporation.
- THF in TEA solution was measured under the conditions of a flow rate of 1.0 mL / min using an RI detector (trade name “HLC8020” manufactured by Tosoh Corporation) to obtain a chromatogram.
- Silica-based column GPC measurement conditions THF was used as an eluent, and 200 ⁇ L of a sample was injected into the apparatus for measurement.
- the column uses the product names “Zorbax PSM-1000S”, “PSM-300S”, and “PSM-60S”, and uses the product name “DIOL 4.6 ⁇ 12.5 mm 5 micron” as a guard column in the preceding stage. Connected and used.
- a chromatogram was obtained by measurement using a RI detector (trade name “HLC8020” manufactured by Tosoh Corporation) under conditions of a column oven temperature of 40 ° C. and a THF flow rate of 0.5 mL / min.
- An RI detector (trade name “HLC8020” manufactured by Tosoh Corporation) was used under the conditions of an oven temperature of 40 ° C. and a THF in TEA flow rate of 1.0 mL / min. 10 mg of a sample for measurement was dissolved in 20 mL of THF to prepare a measurement solution, and 200 ⁇ L of the measurement solution was injected into a GPC measurement device and measured.
- a mixed solution of tetrahydrofuran and triethylamine (THF in TEA: 5 mL of triethylamine was mixed with 1 L of tetrahydrofuran to prepare) was used.
- the column used was a guard column: trade name “TSKguardcolumn HHR-H” manufactured by Tosoh Corporation and a column: trade name “TSKgel G6000HHR”, “TSKgel G5000HHR”, “TSKgel G4000HHR” manufactured by Tosoh Corporation.
- a GPC-light scattering measurement apparatus (trade name “Viscotek TDAmax” manufactured by Malvern) was used under the conditions of an oven temperature of 40 ° C.
- THF flow rate 1.0 mL / min. 10 mg of a sample for measurement was dissolved in 20 mL of THF to prepare a measurement solution, and 200 ⁇ L of the measurement solution was injected into a GPC measurement device and measured.
- the column used was a guard column: trade name “TSKguardcolumn HHR-H” manufactured by Tosoh Corporation and a column: trade name “TSKgel G6000HHR”, “TSKgel G5000HHR”, “TSKgel G4000HHR” manufactured by Tosoh Corporation.
- a GPC-light scattering measurement device (trade name “Viscotek TDAmax” manufactured by Malvern) equipped with a viscosity detector was used under the conditions of an oven temperature of 40 ° C. and a THF flow rate of 1.0 mL / min. 10 mg of a sample for measurement was dissolved in 20 mL of THF to prepare a measurement solution, and 200 ⁇ L of the measurement solution was injected into a GPC measurement device and measured.
- Nitrogen content (mass ppm) Using a modified conjugated diene polymer as a sample, in accordance with JIS-2609: Crude oil and petroleum products-nitrogen content test method, chemiluminescence method, trace total nitrogen analyzer ("TN-2100H” manufactured by Mitsubishi Chemical Analytech Co., Ltd.) The emission intensity at 590-2500 nm is detected by oxidizing the nitrogen monoxide produced by the thermal decomposition of the sample with oxygen gas under the flow of argon gas and then oxidizing with ozone gas under dehydrating conditions. And the nitrogen content was determined from the area value of the issuance strength.
- Glass transition temperature (Tg) Glass transition temperature (Tg) Using a modified conjugated diene polymer as a sample, in accordance with ISO 22768: 2006, using a differential scanning calorimeter (trade name “DSC3200S” manufactured by Mac Science Co., Ltd.), from ⁇ 100 ° C. under a flow of helium at 50 mL / min. The DSC curve was recorded while the temperature was raised at 20 ° C./min, and the peak top (Inflection point) of the DSC differential curve was taken as the glass transition temperature.
- DSC3200S differential scanning calorimeter
- Example 1 Modified Conjugated Diene Polymer (Sample A) The internal volume is 10 L, the ratio of internal height (L) to diameter (D) (L / D) is 4.0, has an inlet at the bottom, has an outlet at the top, a stirrer and Two autoclaves having a temperature adjusting jacket were connected.
- one static mixer connected downstream of the second reactor outlet, 1,3-butadiene from which impurities such as moisture had been removed in advance, 18.9 g / min, styrene 10.6 g / min, n-hexane Were mixed at 180.2 g / min.
- n-butyllithium for impurity inactivation treatment is supplied at 0.087 mmol / min and mixed with a static mixer, and then the bottom of the first reactor is added. Continuously fed.
- 2,2-bis (2-oxolanyl) propane as a polar substance is also referred to as piperidinolithium (“1-lithiopiperidine”) as a lithium amide prepared in advance as a polymerization initiator at a rate of 0.018 g / min.
- LA-1 abbreviated as “LA-1”) and n-butyllithium (molar ratio of piperidinolithium and n-butyllithium was 0.75: 0.25) was added to 0.180 mmol. / Min was fed to the bottom of the first reactor, and the reactor internal temperature was maintained at 67 ° C. The polymer solution was continuously withdrawn from the top of the first reactor, continuously fed to the bottom of the second reactor, and the reaction was continued at 72 ° C., and further fed to the static mixer from the top of the second reactor.
- a small amount of the copolymer solution before the addition of the modifier is withdrawn from the outlet of the second reactor, an antioxidant (BHT) is added so as to be 0.2 g per 100 g of the polymer, and then the solvent is removed.
- BHT antioxidant
- the Mooney viscosity was measured and found to be 62.
- Example 2 Modified Conjugated Diene Polymer
- AS-2 2,2-Dimethoxy-1- (3-trimethoxysilylpropyl) -1-aza-2-silacyclopentane is tris (3-trimethoxysilylpropyl) amine (abbreviated as “AS-2” in the table).
- Sample B was obtained in the same manner as in Example 1 except that the amount added was changed to 0.032 mmol / min. Table 1 shows the physical properties of Sample B.
- Example 3 Modified Conjugated Diene Polymer (Sample C) 2,2-Dimethoxy-1- (3-trimethoxysilylpropyl) -1-aza-2-silacyclopentane is replaced with bis (3- (methylamino) propyl) trimethoxysilane (in the table, “AS-3”). Sample C was obtained in the same manner as in Example 1 except that the amount added was changed to 0.048 mmol / min. Table 1 shows the physical properties of Sample C.
- Example 4 Modified Conjugated Diene Polymer (Sample D)
- the 1,3-butadiene of Example 1 was changed to 20.2 g / min, styrene was changed to 11.3 g / min, and n-hexane was changed to 177.4 g / min, and the internal temperature of the first reactor was maintained at 70 ° C. did.
- the polymer solution is continuously withdrawn from the top of the first reactor and continuously supplied to the bottom of the second reactor and the reaction is continued at 76 ° C., and n-butyllithium is added for impurity deactivation treatment.
- Example 5 Modified Conjugated Diene Polymer (Sample E) Sample E was obtained in the same manner as in Example 1, except that piperidinolithium was replaced with (4- (piperidinyl) -2-butenyl) lithium (abbreviated as “LA-2” in the table). Table 1 shows the physical properties of Sample E.
- Example 6 Modified Conjugated Diene Polymer (Sample F) Sample F was obtained in the same manner as in Example 1, except that piperidinolithium was replaced with hexamethyleneiminolithium (abbreviated as “LA-3” in the table). Table 1 shows the physical properties of Sample F.
- Example 7 Modified Conjugated Diene Polymer (Sample G) Sample G was obtained in the same manner as in Example 1, except that piperidinolithium was replaced with N, N-dimethyl-o-toluidinolithium (abbreviated as “LA-4” in the table). Table 1 shows the physical properties of Sample G.
- Example 8 Modified Conjugated Diene Polymer (Sample H) Piperidinolithium is 2- (2-methylpiperidinyl) -1-ethyllithium (abbreviated as “LA-5” in the table, trade name “AI-250” manufactured by FMC). Sample H was obtained in the same manner as in Example 1 except that the sample H was changed. Table 1 shows the physical properties of Sample H.
- Example 9 Modified Conjugated Diene Polymer (Sample I)
- the 1,3-butadiene of Example 1 was changed to 21.7 g / min, styrene was changed to 12.2 g / min, and n-hexane was changed to 176.4 g / min, and the internal temperature of the first reactor was maintained at 72 ° C. did.
- the polymer solution is continuously withdrawn from the top of the first reactor and continuously supplied to the bottom of the second reactor and the reaction is continued at 78 ° C., and n-butyllithium is added for impurity deactivation treatment.
- Example 10 Modified Conjugated Diene Polymer (Sample J) The addition amount of the polar substance 2,2-bis (2-oxolanyl) propane was changed to 0.028 g / min, the first reactor internal temperature was kept at 73 ° C., and the second reactor internal temperature was 80 ° C. Sample J was obtained in the same manner as in Example 9 except that the reaction was continued at ° C. Table 1 shows the physical properties of Sample J.
- Example K Modified Conjugated Diene Polymer
- Sample K was obtained in the same manner as in Example 1 except that piperidinolithium was replaced with normal butyllithium.
- Table 2 shows the physical properties of Sample K.
- Example L Modified Conjugated Diene Polymer
- the addition amount of the polar substance 2,2-bis (2-oxolanyl) propane was changed to 0.027 g / min, the first reactor internal temperature was kept at 81 ° C., and the second reactor internal temperature was 86 ° C.
- Sample L was obtained in the same manner as in Example 1 except that the reaction was continued at ° C. Table 2 shows the physical properties of Sample L.
- Example M Modified Conjugated Diene Polymer
- 1,3-butadiene of Example 1 to 21.7 g / min, styrene to 12.2 g / min, n-hexane to 176.4 g / min, and add n-butyllithium for impurity deactivation treatment
- the amount was changed to 0.079 mmol / min
- the addition amount of the polar substance was changed to 0.022 g / min
- the addition amount of the mixed solution of piperidinolithium and n-butyllithium was changed to 0.354 mmol.
- the reactor internal temperature was maintained at 70 ° C.
- solid content is a value determined by the feed amount of butadiene and styrene as monomers and the solvent, and the mass of all monomers with respect to the total amount (100% by mass) of all monomers and solvent. It calculated
- the “concentration of lithium amide in the solvent” is the concentration of lithium amide used in Examples 1 to 10 and Comparative Examples 1 to 8, and was determined as the ratio (mol / L) of various lithium amides to the solvent. .
- the “monomer concentration during the modification reaction” is a ratio (mass ppm) of the mass of the conjugated diene compound to the total amount of the monomer and the polymer, and in various samples by gas chromatography (GC). The amount of the conjugated diene compound (styrene and butadiene) remaining in was measured.
- Rubber compositions Rubber compositions containing raw rubbers according to the following formulation, using the samples shown in Tables 1 and 2 (samples A to R) as raw rubbers.
- Got. Raw rubber modified conjugated diene polymer (samples A to R)): 100.0 parts by mass Filler 1 (Silica (trade name “Ultrasil 7000GR” manufactured by Evonik Degussa)): 75.0 parts by mass Filler 2 (Carbon black (trade name “Seast KH (N339)” manufactured by Tokai Carbon Co., Ltd.)): 5.0 parts by mass Silane coupling agent (trade name “Si75” manufactured by Evonik Degussa): 6.0 parts by mass Process oil (S-RAE oil (trade name “JOMO process NC140” manufactured by Japan Energy)): 30.0 parts by mass Wax (trade name “Sannok N” manufactured by Ouchi Shinsei Chemical): 1.5 parts by mass : 2.5 parts by mass
- S-RAE oil trade name “JOMO process NC
- the above materials were kneaded by the following method to obtain a rubber composition.
- a closed kneader (with an internal volume of 0.3 L) equipped with a temperature control device, the raw rubber (samples A to R) under the conditions of a filling rate of 65% and a rotor rotational speed of 50/57 rpm as the first stage kneading , Fillers 1 and 2 (silica, carbon black), silane coupling agent, process oil, wax, zinc white, and stearic acid were kneaded.
- the temperature of the closed mixer was controlled, and each rubber composition was obtained at a discharge temperature (compound) of 155 to 160 ° C.
- the mixture obtained above was cooled to room temperature, an anti-aging agent was added, and the mixture was kneaded again to improve silica dispersion. Also in this case, the discharge temperature (formulation) was adjusted to 155 to 160 ° C. by controlling the temperature of the mixer.
- sulfur and vulcanization accelerators 1 and 2 were added and kneaded with an open roll set at 70 ° C. Thereafter, it was molded and vulcanized with 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 method. The results are shown in Tables 3 and 4.
- Viscoelastic Parameters Viscoelastic Parameters Viscoelastic parameters were measured in a torsion mode using a viscoelasticity tester (ARES-G2) manufactured by TA Instruments Japan. Each measured value was indexed with the result of Comparative Example 9 as 100. Tan ⁇ measured at 0 ° C. with a frequency of 10 Hz and a strain of 1% was used as an index of wet grip performance. A larger value indicates better wet grip performance. Further, tan ⁇ measured at 50 ° C. with a frequency of 10 Hz and a strain of 3% was used as an index of fuel saving characteristics. The smaller the value, the better the fuel saving performance.
- the modified conjugated diene polymer compositions of Examples 11 to 20 have a lower tan ⁇ at 50 ° C. and less hysteresis loss than the compositions of Comparative Examples 9 to 16, Low rolling resistance of the tire was realized, tan ⁇ at 0 ° C. was high, and at least it was confirmed that wet skid resistance was excellent. Furthermore, it was at least confirmed that the modified conjugated diene polymer compositions of Examples 11 to 20 had practically sufficient processability (formulation Mooney viscosity), abrasion resistance, and tensile properties.
- the modified conjugated diene polymer according to the present invention has industrial applicability in fields such as tire treads, automobile interior / exterior products, anti-vibration rubber, belts, footwear, foams, and various industrial products.
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Abstract
Description
[1]
110℃において測定されるムーニー緩和率が、0.45以下であり、
変性率が、75質量%以上である、変性共役ジエン系重合体。
[2]
窒素原子を有し、
前記窒素原子の含有量が、前記変性共役ジエン系重合体の総量に対して、25質量ppm以上である、[1]に記載の変性共役ジエン系重合体。
[3]
少なくとも1つの末端に窒素原子を有し、
窒素原子含有アルコキシシラン置換基を中心とする星形高分子構造を有する、[1]又は[2]に記載の変性共役ジエン系重合体。
[4]
粘度検出器付きGPC-光散乱法測定により求められる収縮因子(g’)が、0.86以下である、[1]~[3]のいずれかに記載の変性共役ジエン系重合体。
[5]
ゲル浸透クロマトグラフィー測定により求められる第一の数平均分子量に対する、GPC-光散乱法測定により求められる第二の数平均分子量が、1.00以上である、[1]~[4]のいずれかに記載の変性共役ジエン系重合体。
[6]
ゲル浸透クロマトグラフィー測定により求められる第一の重量平均分子量に対する、GPC-光散乱法測定により求められる第二の重量平均分子量が、1.00以上である、[1]~[5]のいずれかに記載の変性共役ジエン系重合体。
[7]
前記第一の数平均分子量が、200000以上2000000以下であり、
前記第一の数平均分子量に対する前記第一の重量平均分子量は、1.50以上3.50以下である、[1]~[6]のいずれかに記載の変性共役ジエン系重合体。
[8]
下記一般式(A)又は(B)で表される、[1]~[7]のいずれかに記載の変性共役ジエン系重合体。
[9]
[1]~[8]のいずれかに記載の変性共役ジエン系重合体の製造方法であって、
分子内に少なくとも1つ窒素原子を有する有機リチウム化合物の存在下、少なくとも共役ジエン化合物を重合し、共役ジエン系重合体を得る重合工程と、
前記共役ジエン系重合体を、1分子中にシリル基に結合したアルコキシ基を4つ以上と3級アミノ基とを有する変性剤により、変性させる変性工程と、を有する、変性共役ジエン系重合体の製造方法。
[10]
前記変性剤は、下記一般式(1)~(3)のいずれかで表される変性剤を含む、[9]に記載の変性共役ジエン系重合体の製造方法。
[11]
前記変性剤は、前記式(1)で表される変性剤を含み、かつ前記式(1)におけるmは2を示しかつnは3を示し、又は、前記式(2)で表される変性剤を含み、かつ前記式(2)におけるm、n、及びlは全て3を示す、[10]に記載の変性共役ジエン系重合体の製造方法。
[12]
前記有機リチウム化合物は、下記一般式(14)~(17)のいずれかで表される有機リチウム化合物を含む、[9]~[11]のいずれかに記載の変性共役ジエン系重合体の製造方法。
[13]
前記重合工程において、重合方式が連続式であり、重合温度が45℃以上80℃以下であり、かつ、ソリッドコンテントが16質量%以下である、[9]~[12]のいずれかに記載の変性共役ジエン系重合体の製造方法。
[14]
前記重合工程において、重合方式が連続式であり、かつ、前記有機リチウム化合物の濃度が炭化水素溶媒の容積に対して0.010mol/L以下である、[9]~[13]のいずれかに記載の変性共役ジエン系重合体の製造方法。
[15]
前記変性工程において、前記共役ジエン化合物の含有量が、単量体及び重合体の総量に対して、100質量ppm以上50000質量ppm以下である、[9]~[14]のいずれかに記載の変性共役ジエン系重合体の製造方法。
[16]
[9~[15のいずれかに記載の変性共役ジエン系重合体の製造方法によって得られる、変性共役ジエン系重合体。
[17]
ゴム成分と、該ゴム成分100質量部に対して0.5質量部以上300質量部以下のシリカ系無機充填剤と、を含み、
前記ゴム成分は、該ゴム成分100質量部に対して、[1]~[8]及び[16]のいずれかに記載の変性共役ジエン系重合体を20質量部以上含む、変性共役ジエン系重合体組成物。
本実施形態の変性共役ジエン系重合体は、110℃において測定されるムーニー緩和率(以下、単に「ムーニー緩和率」又は「MSR」ともいう。)が、0.45以下であり、変性率が、75質量%以上である。
本実施形態の変性共役ジエン系重合体は、分子内に少なくとも1つ窒素原子を有する有機リチウム化合物を重合開始剤として用い、少なくとも共役ジエン化合物を重合し、共役ジエン系重合体を得る重合工程と、該共役ジエン系重合体を、1分子中にシリル基に結合したアルコキシ基を4つ以上と3級アミノ基とを有する変性剤により、変性させる変性工程と、を有する、変性共役ジエン系重合体の製造方法によって得られる。変性共役ジエン系重合体を構成する共役ジエン系重合体は、単一の共役ジエン化合物の単独重合体、異なる種類の共役ジエン化合物の重合体すなわち共重合体、又は共役ジエン化合物と芳香族ビニル化合物との共重合体である。
本実施形態の重合工程は、分子内に少なくとも1つ窒素原子を有する有機リチウム化合物の存在下、少なくとも共役ジエン化合物を重合し、共役ジエン系重合体を得る。
本実施形態の重合開始剤は、分子内に少なくとも1つ窒素原子を有する有機リチウム化合物、又は、分子内に少なくとも1つ窒素原子を有する化合物及び有機リチウム化合物を含む重合開始剤系、を用いることができる。重合開始剤系は、分子内に少なくとも1つ窒素原子を有する有機リチウム化合物を、予め所定の反応器で調製しておいてもよいし、後述する重合又は共重合を行うための反応器中に供給し、重合又は共重合と同時、もしくはその前に、分子内に少なくとも1つ窒素原子を有する化合物と有機リチウムとを反応させてもよい。
(I)式(25)で表される化合物と有機リチウム化合物とを炭化水素溶媒中で反応させ、リチウムアミド化合物を合成する。
(II)炭化水素溶媒中、得られたリチウムアミド化合物と、ブタジエン又はイソプレンとを反応させる。
(III)アルコールを加えてリチウムを失活させ、得られた生成物を減圧蒸留する。
(IV)蒸留して得られた生成物と有機リチウム化合物とを炭化水素溶媒中で反応させる。
上記有機リチウム化合物の調製の際には、系内に極性化合物を添加してもよい。生成の促進及び炭化水素溶媒への可溶化が図れる傾向にある。極性化合物としては、以下のものに限定されないが、例えば、3級モノアミン、3級ジアミン、鎖状エーテル及び環状エーテルが挙げられる。
本実施形態の共役ジエン系重合体は、炭化水素溶媒中で、少なくとも共役ジエン化合物を重合して得られ、共役ジエン化合物と芳香族ビニル化合物とを共重合して得てもよい。共役ジエン系重合体は、分子内に少なくとも1つ窒素原子を有する有機リチウム化合物を重合開始剤とし、連続重合法を用いたアニオン重合反応により成長して得られることが好ましい。特に、共役ジエン系重合体は、リビングアニオン重合による成長反応によって得られる活性末端を有する重合体であることがより好ましい。これにより、高変性率の変性共役ジエン系重合体を得ることができる。
共役ジエン化合物としては、重合可能な単量体であれば以下のものに限定されないが、例えば、1,3-ブタジエン、イソプレン、2,3-ジメチル-1,3-ブタジエン、1,3-ペンタジエン、3-メチル-1,3-ペンタジエン、1,3-ヘプタジエン、及び1,3-ヘキサジエンが挙げられる。これらの中でも、工業的入手の容易さの観点から、1,3-ブタジエン、及びイソプレンが好ましい。これらは1種のみならず2種以上を併用してもよい。
芳香族ビニル化合物としては、共役ジエン化合物と共重合可能な単量体であれば以下のものに限定されないが、例えば、スチレン、p-メチルスチレン、α-メチルスチレン、ビニルエチルベンゼン、ビニルキシレン、ビニルナフタレン、及びジフェニルエチレンが挙げられる。これらの中でも、工業的入手の容易さの観点から、スチレンが好ましい。これらは1種のみならず2種以上を併用してもよい。
重合工程は、溶媒中で重合することが好ましい。溶媒としては、例えば、飽和炭化水素、芳香族炭化水素等の炭化水素系溶媒が挙げられる。具体的な炭化水素系溶媒として、以下のものに限定されないが、例えば、ブタン、ペンタン、ヘキサン、ヘプタン等の脂肪族炭化水素;シクロペンタン、シクロヘキサン、メチルシクロペンタン、メチルシクロヘキサン等の脂環族炭化水素;ベンゼン、トルエン、キシレン等の芳香族炭化水素及びそれらの混合物からなる炭化水素が挙げられる。
本実施形態の変性共役ジエン系重合の製造方法は、共役ジエン系重合体を、1分子中にシリル基に結合したアルコキシ基を4つ以上と3級アミノ基とを有する変性剤により、変性させる変性工程を有する。
本実施形態の変性剤としては、MSRが0.45以下であり、変性率が75質量%以上である変性共役ジエン系重合体を得るために、重合開始剤由来の共役ジエン系重合体における活性末端と反応することで、3分岐以上の多分岐構造、及び該変性工程により珪素原子に結合したアルコキシ基、ハロゲン基、及びアミノ基からなる群より選ばれる少なくとも一つの官能基を、共役ジエン系重合体に導入できる変性剤が好ましい。重合開始剤由来の共役ジエン系重合体における活性末端と反応する、上記変性剤が有する官能基としては、例えば、アルコキシシリル基、シラザン基、及びハロシリル基が挙げられる。上記多分岐構造の分岐数は、変性剤が有する上記官能基の数と変性剤の添加率とで調整することができ、3分岐以上の分岐数が好ましく、4分岐以上の分岐数がより好ましい。変性工程により、共役ジエン系重合体に導入できる官能基としては、珪素原子に結合したアルコキシ基、及びアミノ基がより好ましい。
本実施形態の変性共役ジエン系重合体の製造方法は、さらに脱溶媒工程を有することができる。脱溶媒工程は、変性共役ジエン系重合体を、重合体溶液から取得する工程であり、公知の方法を用いることができる。その方法として、例えば、スチームストリッピング等で溶媒を分離した後、重合体を濾別し、さらにそれを脱水及び乾燥して重合体を取得する方法、フラッシングタンクで濃縮し、さらにベント押し出し機等で脱揮する方法、ドラムドライヤー等で直接脱揮する方法が挙げられる。
本実施形態の変性共役ジエン系重合体は、加硫物として好適に用いられる。加硫物は、例えば、本実施形態の変性共役ジエン系重合体を、必要に応じて、シリカ系無機充填剤、カーボンブラック等の無機充填剤、本実施形態の変性共役ジエン系重合体以外のゴム状重合体、シランカップリング剤、ゴム用軟化剤、ワックス、加硫剤、加硫促進剤、加硫助剤等と混合して、変性共役ジエン系重合体組成物とした後、加熱して加硫することにより得ることができる。これらの変性共役ジエン系重合体組成物の中でも、ゴム成分と、該ゴム成分100質量部に対して0.5質量部以上300質量部以下のシリカ系無機充填剤と、を含み、変性共役ジエン系重合体組成物が好ましい。また、上記ゴム成分が、該ゴム成分100質量部に対して、本実施形態の変性共役ジエン系重合体を20質量部以上含む、変性共役ジエン系重合体組成物とすることがより好ましい。
共役ジエン系重合体組成物を含むゴム成分は、本実施形態の変性共役ジエン系重合体以外のゴム状重合体を、本実施形態の変性共役ジエン系重合体と組み合わせて使用できる。このようなゴム状重合体としては、以下のものに限定されないが、例えば、共役ジエン系重合体又はその水素添加物、共役ジエン系化合物とビニル芳香族化合物とのランダム共重合体又はその水素添加物、共役ジエン系化合物とビニル芳香族化合物とのブロック共重合体又はその水素添加物、非ジエン系重合体、及び天然ゴムが挙げられる。より具体的なゴム状重合体としては、例えば、ブタジエンゴム又はその水素添加物、イソプレンゴム又はその水素添加物、スチレン-ブタジエンゴム又はその水素添加物、スチレン-ブタジエンブロック共重合体又はその水素添加物、及びスチレン-イソプレンブロック共重合体又はその水素添加物等のスチレン系エラストマー、アクリロニトリル-ブタジエンゴム又はその水素添加物が挙げられる。
変性共役ジエン系重合体を試料として、試料100mgをクロロホルムで100mLにメスアップ、溶解して測定サンプルとした。スチレンのフェニル基による紫外線吸収波長(254nm付近)の吸収量により、試料である重合体100質量%に対しての結合スチレン量(質量%)を測定した(島津製作所社製の商品名「UV-2450」)。
変性共役ジエン系重合体を試料として、試料50mgを10mLの二硫化炭素に溶解して測定サンプルとした。溶液セルを用いて、赤外線スペクトルを600~1000cm-1の範囲で測定して、所定の波数における吸光度によりハンプトンの方法の計算式に従いブタジエン部分のミクロ構造、すなわち、1,2-ビニル結合量(mol%)を求めた(日本分光社製の商品名「FT-IR230」)。
変性剤添加前の共重合体、又は変性共役ジエン系重合体を試料として、ムーニー粘度計(上島製作所社製の商品名「VR1132」)を用い、JIS K6300(ISO289-1)及びISO289-4に準拠し、ムーニー粘度及びムーニー緩和率を測定した。測定温度は110℃とした。また、伸展油を用いて伸展した試料の場合には100℃で測定した。まず、試料を1分間予熱した後、2rpmでローターを回転させ、4分後のトルクを測定してムーニー粘度(ML(1+4))とした。その後、変性共役ジエン系重合体を試料とした場合については、即座にローターの回転を停止させ、停止後1.6~5秒間の0.1秒ごとのトルクをムーニー単位で記録し、トルクと時間(秒)を両対数プロットした際の直線の傾きを求め、その絶対値をムーニー緩和率(MSR)とした。
変性共役ジエン系重合体を試料として、シリカ系ゲルを充填剤としたGPCカラムに変性した成分が吸着する特性を応用することにより測定した。試料及び低分子量内部標準ポリスチレンを含む試料溶液を、ポリスチレン系ゲルカラムで測定したクロマトグラムと、シリカ系カラムで測定したクロマトグラムとの差分よりシリカカラムへの吸着量を測定し、変性率を求めた。具体的には、以下に示す通りである。
ポリスチレン系カラムGPC測定条件:THFを溶離液として用い、試料200μLを装置に注入して測定した。カラムは、ガードカラム:東ソー社製の商品名「TSKguardcolumn HHR-H」と、カラム:東ソー社製の商品名「TSKgel SuperMultipore HZ-H」3本とを接続して使用した。カラムオーブン温度:40℃、THF in TEA溶液を流量1.0mL/分の条件で、RI検出器(東ソー社製の商品名「HLC8020」)を用いて測定しクロマトグラムを得た。
シリカ系カラムGPC測定条件:THFを溶離液として用い、試料200μLを装置に注入して測定した。カラムは、商品名「Zorbax PSM-1000S」、「PSM-300S」、及び「PSM-60S」を接続して使用し、その前段にガードカラムとして商品名「DIOL 4.6×12.5mm 5micron」を接続して使用した。カラムオーブン温度40℃、THF流量0.5mL/分の条件で、RI検出器(東ソー社製の商品名「HLC8020」)を用いて測定しクロマトグラムを得た。
変性率の計算方法:ポリスチレン系カラムを用いたクロマトグラムのピーク面積の全体を100として、試料のピーク面積をP1、標準ポリスチレンのピーク面積をP2、シリカ系カラムを用いたクロマトグラムのピーク面積の全体を100として、試料の面積をP3、標準ポリスチレンのピーク面積をP4として、下記式より変性率(%)を求めた。
変性率(%)=[1-(P2×P3)/(P1×P4)]×100
(ただし、P1+P2=P3+P4=100)
変性共役ジエン系重合体を試料として、ポリスチレン系ゲルを充填剤としたカラムを3本連結したGPC測定装置を使用して、クロマトグラムを測定し、標準ポリスチレンを使用して得られる検量線に基づいて重量平均分子量(Mw)と数平均分子量(Mn)を求めた。溶離液はテトラヒドロフラン(THF)を使用した。カラムは、ガードカラム:東ソー社製社製の商品名「TSKguardcolumn HHR-H」、カラム:東ソー社製の商品名「TSKgel SuperMultipore HZ-H」3本とを接続して使用した。オーブン温度40℃、THF in TEA流量1.0mL/分の条件で、RI検出器(東ソー社製の商品名「HLC8020」)を用いた。測定用の試料10mgを20mLのTHFに溶解して測定溶液とし、測定溶液200μLをGPC測定装置に注入して測定した。
変性共役ジエン系重合体を試料として、ポリスチレン系ゲルを充填剤としたカラムを3本連結したGPC-光散乱測定装置を使用して、クロマトグラムを測定し、溶液粘度及び光散乱法に基づいて重量平均分子量(Mw-i)と数平均分子量(Mn-i)とを求めた(「絶対分子量」ともいう。)。溶離液はテトラヒドロフランとトリエチルアミンの混合溶液(THF in TEA:トリエチルアミン5mLをテトラヒドロフラン1Lに混合させ調整した。)を使用した。カラムは、ガードカラム:東ソー社製の商品名「TSKguardcolumn HHR-H」と、カラム:東ソー社製の商品名「TSKgel G6000HHR」、「TSKgel G5000HHR」、「TSKgel G4000HHR」とを接続して使用した。オーブン温度40℃、THF流量1.0mL/分の条件で、GPC-光散乱測定装置(マルバーン社製の商品名「Viscotek TDAmax」)を用いた。測定用の試料10mgを20mLのTHFに溶解して測定溶液とし、測定溶液200μLをGPC測定装置に注入して測定した。
変性共役ジエン系重合体を試料として、ポリスチレン系ゲルを充填剤としたカラムを3本連結した粘度検出器付き、GPC-光散乱測定装置を使用して、クロマトグラムを測定し、溶液粘度及び光散乱法に基づいて分子量を求めた。溶離液はテトラヒドロフランとトリエチルアミンとの混合溶液(THF in TEA:トリエチルアミン5mLをテトラヒドロフラン1Lに混合させ調整した。)を使用した。カラムは、ガードカラム:東ソー社製の商品名「TSKguardcolumn HHR-H」と、カラム:東ソー社製の商品名「TSKgel G6000HHR」、「TSKgel G5000HHR」、「TSKgel G4000HHR」とを接続して使用した。オーブン温度40℃、THF流量1.0mL/分の条件で粘度検出器付き、GPC-光散乱測定装置(マルバーン社製の商品名「Viscotek TDAmax」)を用いた。測定用の試料10mgを20mLのTHFに溶解して測定溶液とし、測定溶液200μLをGPC測定装置に注入して測定した。得られた測定サンプルの固有粘度と分子量を、固有粘度と分子量の関係式([η][η]=KMα([η]:固有粘度、M:分子量)における定数(K、α)を、logK=-3.883、α=0.771として、分子量Mの範囲を1000~20000000まで入力して作成した標準固有粘度[η]0と分子量Mとの関係に対して、各分子量Mでの固有粘度[η]を標準固有粘度[η]0に対する固有粘度[η]の関係として[η]/[η]0を各分子量Mで算出し、その平均値を収縮因子(g’)とした。
変性共役ジエン系重合体を試料として、JIS-2609:原油及び石油製品―窒素分試験方法、化学発光法に準拠して、微量全窒素分析装置(三菱化学アナリテック社製 「TN-2100H」)を用い、アルゴンガスの流通下、試料中を熱分解した後に酸素ガスにより燃焼酸化して生成する一酸化窒素を脱水分条件下でオゾンガスと酸化反応をさせて検出される590~2500nmにおける発光強度を測定し、その発行強度の面積値から窒素含有量を求めた。
変性共役ジエン系重合体を試料として、ISO 22768:2006に準拠して、示差走査熱量計(マックサイエンス社製の商品名「DSC3200S」)を用い、ヘリウム50mL/分の流通下、-100℃から20℃/分で昇温しながらDSC曲線を記録し、DSC微分曲線のピークトップ(Inflection point)をガラス転移温度とした。
内容積が10Lであり、内部の高さ(L)と直径(D)との比(L/D)が4.0であり、底部に入口を有し、頂部に出口を有し、攪拌機および温度調整用のジャケットを有するオートクレーブを2基連結した。さらに、2基目の反応器出口下流にスタティックミキサーを1基連結した予め水分等の不純物を除去した1,3-ブタジエンを、18.9g/分、スチレンを10.6g/分、n-ヘキサンを180.2g/分で混合した。この混合溶液が1基目の反応器に入る直前で、不純物不活性化処理用のn-ブチルリチウムを0.087mmol/分で供給しスタティックミキサーで混合した後、1基目の反応器の底部に連続的に供給した。更に、極性物質として2,2-ビス(2-オキソラニル)プロパンを0.018g/分の速度で、重合開始剤として、予め調整したリチウムアミドとしてピペリジノリチウム(「1-リチオピペリジン」ともいう。表中、「LA-1」と略す。)とn-ブチルリチウムの混合溶液(ピペリジノリチウムとn-ブチルリチウムのモル比は0.75:0.25とした)を、0.180mmol/分の速度で、1基目反応器の底部へ供給し、反応器内温を67℃に保持した。1基目反応器頂部より重合体溶液を連続的に抜き出し、2基目反応器の底部に連続的に供給し72℃で反応を継続し、さらに2基目の頂部よりスタティックミキサーへ供給した。2基目反応器出口より、変性剤添加前の共重合体溶液を少量抜き出し、酸化防止剤(BHT)をポリマー100gあたり、0.2gとなるように添加した後に溶媒を除去し、110℃のムーニー粘度を測定した結果、62であった。
2,2-ジメトキシ-1-(3-トリメトキシシリルプロピル)-1-アザ-2-シラシクロペンタンをトリス(3-トリメトキシシリルプロピル)アミン(表中、「AS-2」と略す。)に替え、その添加量を0.032mmol/分に変えた以外は、実施例1と同様にして、試料Bを得た。試料Bの物性を表1に示す。
2,2-ジメトキシ-1-(3-トリメトキシシリルプロピル)-1-アザ-2-シラシクロペンタンをビス(3-(メチルアミノ)プロピル)トリメトキシシラン(表中、「AS-3」と略す。)に替え、その添加量を0.048mmol/分に変えた以外は、実施例1と同様にして、試料Cを得た。試料Cの物性を表1に示す。
実施例1の1,3-ブタジエンを、20.2g/分、スチレンを11.3g/分、n-ヘキサンを177.4g/分に変え、1基目の反応器内温を70℃に保持した。1基目反応器頂部より重合体溶液を連続的に抜き出し、2基目反応器の底部に連続的に供給し76℃で反応を継続し、不純物不活性化処理用のn-ブチルリチウムの添加量を0.093mmol/分に変え、極性物質の添加量を0.022g/分に変え、ピペリジノリチウムとn-ブチルリチウムの混合溶液の添加量を0.192mmolに変え、2,2-ジメトキシ-1-(3-トリメトキシシリルプロピル)-1-アザ-2-シラシクロペンタンの添加量を0.050mmol/分に変えた以外は、実施例1と同様にして、試料Dを得た。試料Dの物性を表1に示す。
ピペリジノリチウムを(4-(ピペリジニル)-2-ブテニル)リチウム(表中、「LA-2」と略す。)に替えた以外は、実施例1と同様にして、試料Eを得た。試料Eの物性を表1に示す。
ピペリジノリチウムをヘキサメチレンイミノリチウム(表中、「LA-3」と略す。)に替えた以外は、実施例1と同様にして、試料Fを得た。試料Fの物性を表1に示す。
ピペリジノリチウムをN,N-ジメチル-o-トルイジノリチウム(表中、「LA-4」と略す。)に替えた以外は、実施例1と同様にして、試料Gを得た。試料Gの物性を表1に示す。
ピペリジノリチウムを、2-(2-メチルピペリジニル)-1-エチルリチウム(表中、「LA-5」と略す。FMC社製の商品名「AI-250」)。)に替えた以外は、実施例1と同様にして、試料Hを得た。試料Hの物性を表1に示す。
実施例1の1,3-ブタジエンを、21.7g/分、スチレンを12.2g/分、n-ヘキサンを176.4g/分に変え、1基目の反応器内温を72℃に保持した。1基目反応器頂部より重合体溶液を連続的に抜き出し、2基目反応器の底部に連続的に供給し78℃で反応を継続し、不純物不活性化処理用のn-ブチルリチウムの添加量を0.099mmol/分に変え、極性物質の添加量を0.026g/分に変え、ピペリジノリチウムとn-ブチルリチウムの混合溶液の添加量を0.213mmolに変え、2,2-ジメトキシ-1-(3-トリメトキシシリルプロピル)-1-アザ-2-シラシクロペンタンの添加量を0.056mmol/分に変えた以外は、実施例1と同様にして、試料Dを得た。試料Iの物性を表1に示す。
極性物質2,2-ビス(2-オキソラニル)プロパンの添加量を0.028g/分に変え、1基目の反応器内温を73℃に保持し、2基目の反応器内温を80℃で反応を継続した以外は、実施例9と同様にして、試料Jを得た。試料Jの物性を表1に示す。
ピペリジノリチウムをノルマルブチルリチウムに替えた以外は、実施例1と同様にして、試料Kを得た。試料Kの物性を表2に示す。
極性物質2,2-ビス(2-オキソラニル)プロパンの添加量を0.027g/分に変え、1基目の反応器内温を81℃に保持し、2基目の反応器内温を86℃で反応を継続した以外は、実施例1と同様にして、試料Lを得た。試料Lの物性を表2に示す。
実施例1の1,3-ブタジエンを、21.7g/分、スチレンを12.2g/分、n-ヘキサンを176.4g/分に変え、不純物不活性化処理用のn-ブチルリチウムの添加量を0.079mmol/分に変え、極性物質の添加量を0.022g/分に変え、ピペリジノリチウムとn-ブチルリチウムの混合溶液の添加量を0.354mmolに変え、1基目の反応器内温を70℃に保持した。1基目反応器頂部より重合体溶液を連続的に抜き出し、2基目反応器の底部に連続的に供給し76℃で反応を継続し、2,2-ジメトキシ-1-(3-トリメトキシシリルプロピル)-1-アザ-2-シラシクロペンタンの添加量を0.093mmol/分に変えた以外は、実施例1と同様にして、試料Mを得た。試料Mの物性を表2に示す。
1,3-ブタジエンを、22.9g/分、スチレンを12.9g/分、n-ヘキサンを173.7g/分に変え、不純物不活性化処理用のn-ブチルリチウムの添加量を0.095mmol/分に変え、極性物質2,2-ビス(2-オキソラニル)プロパンの添加量を0.027g/分に変え、ピペリジノリチウムとn-ブチルリチウムの混合溶液の添加量を0.229mmol/分に変え、1基目の反応器内温を71℃に保持した。1基目反応器頂部より重合体溶液を連続的に抜き出し、2基目反応器の底部に連続的に供給し77℃で反応を継続し、2,2-ジメトキシ-1-(3-トリメトキシシリルプロピル)-1-アザ-2-シラシクロペンタンの添加量を0.057mmol/分に変えた以外は、実施例1と同様にして、試料Nを得た。試料Nの物性を表2に示す。
極性物質2,2-ビス(2-オキソラニル)プロパンの添加量を0.016g/分に変え、ピペリジノリチウムをノルマルブチルリチウムに替え、2,2-ジメトキシ-1-(3-トリメトキシシリルプロピル)-1-アザ-2-シラシクロペンタンをトリス(3-トリメトキシシリルプロピル)アミンに替え、その添加量を0.032mmol/分に変えた以外は、実施例1と同様にして、試料Oを得た。試料Oの物性を表2に示す。
極性物質2,2-ビス(2-オキソラニル)プロパンの添加量を0.032g/分に変え、1基目の反応器内温を76℃に保持し、2基目の反応器内温を85℃で反応を継続し、2,2-ジメトキシ-1-(3-トリメトキシシリルプロピル)-1-アザ-2-シラシクロペンタンをトリス(3-トリメトキシシリルプロピル)アミンに替え、その添加量を0.048mmol/分に変えた以外は、実施例1と同様にして、試料Pを得た。試料Pの物性を表2に示す。
極性物質2,2-ビス(2-オキソラニル)プロパンの添加量を0.035g/分に変え、1基目の反応器内温を76℃に保持し、2基目の反応器内温を88℃で反応を継続し、2,2-ジメトキシ-1-(3-トリメトキシシリルプロピル)-1-アザ-2-シラシクロペンタンをビス(3-(メチルアミノ)プロピル)トリメトキシシランに替え、その添加量を0.072mmol/分に変えた以外は、実施例1と同様にして試料Qを得た。試料Qの物性を表2に示す。
1,3-ブタジエンを、22.9g/分、スチレンを12.9g/分、n-ヘキサンを173.7g/分に変え、不純物不活性化処理用のn-ブチルリチウムの添加量を0.096mmol/分に変え、極性物質2,2-ビス(2-オキソラニル)プロパンの添加量を0.020g/分に変え、ピペリジノリチウムとn-ブチルリチウムの混合溶液の添加量を0.229mmol/分に変え、2,2-ジメトキシ-1-(3-トリメトキシシリルプロピル)-1-アザ-2-シラシクロペンタンをトリス(3-トリメトキシシリルプロピル)アミンに替え、その添加量を0.057mmol/分に変えた重合を行う以外は、実施例1と同様にして、試料Rを得た。試料Rの物性を表2に示す。
表1及び表2に示す試料(試料A~R)を原料ゴムとして、以下に示す配合に従い、それぞれ原料ゴムを含有するゴム組成物を得た。
原料ゴム(変性共役ジエン系重合体(試料A~R)):100.0質量部
充填剤1(シリカ(エボニック デグサ社製の商品名「Ultrasil 7000GR」)):75.0質量部
充填剤2(カーボンブラック(東海カーボン社製の商品名「シーストKH(N339)」)):5.0質量部
シランカップリング剤(エボニック デグサ社製の商品名「Si75」):6.0質量部
プロセスオイル(S-RAEオイル(ジャパンエナジー社製の商品名「JOMOプロセスNC140」)):30.0質量部
ワックス(大内新興化学社製の商品名「サンノックN」):1.5質量部
亜鉛華:2.5質量部
ステアリン酸:2.0質量部
老化防止剤(N-イソプロピル-N’-フェニル-p-フェニレンジアミン):2.0質量部
硫黄:1.8質量部、
加硫促進剤1(N-シクロヘキシル-2-ベンゾチアジルスルフィンアミド):1.7質量部
加硫促進剤2(ジフェニルグアニジン):2.0質量部
合計:229.5質量部
上記で得た第二段の混練後、かつ、第三段の混練前の配合物を試料として、ムーニー粘度計を使用し、JIS K6300-1に準じて、130℃、1分間の予熱を行った後に、ローターを毎分2回転で4分間回転させた後の粘度を測定し、比較例9の結果を100として指数化した。値が小さいほど加工性に優れることを示す。
ティー・エイ・インスツルメント・ジャパン社製の粘弾性試験機(ARES-G2)を使用し、ねじりモードで粘弾性パラメータを測定した。各々の測定値は、比較例9の結果を100として指数化した。0℃において周波数10Hz、ひずみ1%で測定したtanδをウェットグリップ性能の指標とした。値が大きいほどウェットグリップ性能が良好であることを示す。また、50℃において周波数10Hz、ひずみ3%で測定したtanδを省燃費特性の指標とした。値が小さいほど省燃費性能が良好であることを示す。
JIS K6251の引張試験法に準じて東洋精機製作所製の全自動引張試験機ストログラフAEを使用し、破断強度及び引張伸びを測定した。いずれも比較例9の結果を100として指数化した。数値が大きいほど耐破壊性に優れることを示す。
アクロン摩耗試験機(安田精機製作所製)を使用し、JIS K6264-2に準じて、荷重44.1N、1000回転の摩耗量を測定し、比較例9の結果を100として指数化した。指数が大きいほど耐摩耗性に優れることを示す。
Claims (17)
- 110℃において測定されるムーニー緩和率が、0.45以下であり、
変性率が、75質量%以上である、変性共役ジエン系重合体。 - 窒素原子を有し、
前記窒素原子の含有量が、前記変性共役ジエン系重合体の総量に対して、25質量ppm以上である、請求項1に記載の変性共役ジエン系重合体。 - 少なくとも1つの末端に窒素原子を有し、
窒素原子含有アルコキシシラン置換基を中心とする星形高分子構造を有する、請求項1又は2に記載の変性共役ジエン系重合体。 - 粘度検出器付きGPC-光散乱法測定により求められる収縮因子(g’)が、0.86以下である、請求項1~3のいずれか一項に記載の変性共役ジエン系重合体。
- ゲル浸透クロマトグラフィー測定により求められる第一の数平均分子量に対する、GPC-光散乱法測定により求められる第二の数平均分子量が、1.00以上である、請求項1~4のいずれか一項に記載の変性共役ジエン系重合体。
- ゲル浸透クロマトグラフィー測定により求められる第一の重量平均分子量に対する、GPC-光散乱法測定により求められる第二の重量平均分子量が、1.00以上である、請求項1~5のいずれか一項に記載の変性共役ジエン系重合体。
- 前記第一の数平均分子量が、200000以上2000000以下であり、
前記第一の数平均分子量に対する前記第一の重量平均分子量は、1.50以上3.50以下である、請求項1~6のいずれか一項に記載の変性共役ジエン系重合体。 - 下記一般式(A)又は(B)で表される、請求項1~7のいずれか一項に記載の変性共役ジエン系重合体。
- 請求項1~8のいずれか一項に記載の変性共役ジエン系重合体の製造方法であって、
分子内に少なくとも1つ窒素原子を有する有機リチウム化合物の存在下、少なくとも共役ジエン化合物を重合し、共役ジエン系重合体を得る重合工程と、
前記共役ジエン系重合体を、1分子中にシリル基に結合したアルコキシ基を4つ以上と3級アミノ基とを有する変性剤により、変性させる変性工程と、を有する、変性共役ジエン系重合体の製造方法。 - 前記変性剤は、下記一般式(1)~(3)のいずれかで表される変性剤を含む、請求項9に記載の変性共役ジエン系重合体の製造方法。
- 前記変性剤は、前記式(1)で表される変性剤を含み、かつ前記式(1)におけるmは2を示しかつnは3を示し、又は、前記式(2)で表される変性剤を含み、かつ前記式(2)におけるm、n、及びlは全て3を示す、請求項10に記載の変性共役ジエン系重合体の製造方法。
- 前記有機リチウム化合物は、下記一般式(14)~(17)のいずれかで表される有機リチウム化合物を含む、請求項9~11のいずれか一項に記載の変性共役ジエン系重合体の製造方法。
- 前記重合工程において、重合方式が連続式であり、重合温度が45℃以上80℃以下であり、かつ、ソリッドコンテントが16質量%以下である、請求項9~12のいずれか一項に記載の変性共役ジエン系重合体の製造方法。
- 前記重合工程において、重合方式が連続式であり、かつ、前記有機リチウム化合物の濃度が炭化水素溶媒の容積に対して0.010mol/L以下である、請求項9~13のいずれか一項に記載の変性共役ジエン系重合体の製造方法。
- 前記変性工程において、前記共役ジエン化合物の含有量が、単量体及び重合体の総量に対して、100質量ppm以上50000質量ppm以下である、請求項9~14のいずれか一項に記載の変性共役ジエン系重合体の製造方法。
- 請求項9~15のいずれか一項に記載の変性共役ジエン系重合体の製造方法によって得られる、変性共役ジエン系重合体。
- ゴム成分と、該ゴム成分100質量部に対して0.5質量部以上300質量部以下のシリカ系無機充填剤と、を含み、
前記ゴム成分は、該ゴム成分100質量部に対して、請求項1~8及び16のいずれか一項に記載の変性共役ジエン系重合体を20質量部以上含む、変性共役ジエン系重合体組成物。
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US11780994B2 (en) * | 2018-10-04 | 2023-10-10 | Bridgestone Corporation | Rubber composition, tread rubber, and tire |
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JP7315686B2 (ja) | 2019-09-05 | 2023-07-26 | 旭化成株式会社 | 共役ジエン系重合体、共役ジエン系重合体の製造方法、共役ジエン系重合体組成物、及びゴム組成物。 |
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US20180037674A1 (en) | 2018-02-08 |
US10766972B2 (en) | 2020-09-08 |
JP6908662B2 (ja) | 2021-07-28 |
HUE044416T2 (hu) | 2019-10-28 |
KR102160548B1 (ko) | 2020-09-28 |
EP3260476B1 (en) | 2019-05-08 |
EP3260476A4 (en) | 2018-01-03 |
KR20190060893A (ko) | 2019-06-03 |
SG11201706426YA (en) | 2017-09-28 |
CN107250172A (zh) | 2017-10-13 |
KR20170102320A (ko) | 2017-09-08 |
KR102160548B9 (ko) | 2022-02-18 |
CN107250172B (zh) | 2021-04-09 |
TWI607026B (zh) | 2017-12-01 |
TW201708272A (zh) | 2017-03-01 |
EP3260476A1 (en) | 2017-12-27 |
JPWO2016133202A1 (ja) | 2017-11-02 |
BR112017016522A2 (ja) | 2018-04-10 |
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