WO2018092843A1 - Modified conjugate diene-based polymer production method, modified conjugate diene-based polymer, polymer composition, crosslinked product, and tire - Google Patents

Modified conjugate diene-based polymer production method, modified conjugate diene-based polymer, polymer composition, crosslinked product, and tire Download PDF

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Publication number
WO2018092843A1
WO2018092843A1 PCT/JP2017/041264 JP2017041264W WO2018092843A1 WO 2018092843 A1 WO2018092843 A1 WO 2018092843A1 JP 2017041264 W JP2017041264 W JP 2017041264W WO 2018092843 A1 WO2018092843 A1 WO 2018092843A1
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conjugated diene
compound
polymer
butadiene
polymerization
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PCT/JP2017/041264
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French (fr)
Japanese (ja)
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真 竹内
裕 永田
寛文 千賀
春崇 中森
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Jsr株式会社
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Publication of WO2018092843A1 publication Critical patent/WO2018092843A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
    • C08F297/02—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type
    • 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
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes

Definitions

  • the present disclosure relates to a method for producing a modified conjugated diene polymer, a modified conjugated diene polymer, a polymer composition, a crosslinked product, and a tire.
  • a conjugated diene polymer obtained by polymerization using a conjugated diene compound has good properties such as heat resistance, wear resistance, mechanical strength, and moldability, so that a pneumatic tire, a vibration-proof rubber, Widely used in various industrial products such as hoses.
  • conjugated diene rubber used for tire use at least one end is an isoprene block having 70% by mass or more of isoprene monomer units, and the other end is a conjugated diene polymer chain having an active end; Conjugated diene rubbers obtained by reacting with specific modifiers have been proposed (see, for example, Patent Documents 3 and 4).
  • the present disclosure has been made in view of the above problems, and is a modified conjugated diene-based heavy polymer that can provide a vulcanized rubber that is excellent in processability of the rubber composition and that is excellent in low fuel consumption performance, wear resistance, and wet grip characteristics.
  • One purpose is to provide coalescence.
  • modified conjugated diene polymer production method modified conjugated diene polymer, polymer composition, cross-linked product and tire are provided.
  • a conjugated diene block formed by polymerizing a conjugated diene compound is bonded to both ends of a copolymer chain having a conjugated diene unit and an aromatic vinyl unit, and one of the conjugated dienes
  • the block is a butadiene block formed by polymerizing 1,3-butadiene, has a nitrogen-containing group at the terminal not bonded to the copolymer chain
  • the other conjugated diene block is A modified conjugated diene polymer having a functional group that interacts with silica at a terminal not bonded to a copolymer chain.
  • a modified conjugated diene polymer obtained by polymerizing an aromatic vinyl compound [3] In the presence of a polymer chain having a nitrogen-containing group at one end of a conjugated diene block formed by polymerizing 1,3-butadiene and the other end being an active end, A modified conjugated diene polymer obtained by polymerizing an aromatic vinyl compound. [4] A polymer composition comprising the modified conjugated diene polymer obtained by the production method of [1], or the modified conjugated diene polymer of [2] or [3], an inorganic filler, and a crosslinking agent. object. [5] A crosslinked product obtained by crosslinking the polymer composition of [4]. [6] A tire formed using the cross-linked product of [5].
  • a modified conjugated diene polymer that provides a vulcanized rubber that is excellent in processability of the rubber composition and that is excellent in low fuel consumption performance, wear resistance, and wet grip characteristics.
  • the modified conjugated diene polymer of the present disclosure has a nitrogen-containing group at one end of a polymer chain formed by polymerizing 1,3-butadiene as a polymerization initiator (hereinafter also referred to as “butadiene block”). And is obtained by polymerization using a modified conjugated diene initiator having the other end as an active end.
  • the modified conjugated diene polymer can be produced by a method including the following step A and step B.
  • This step is a step of preparing a modified conjugated diene initiator, which is a polymerization initiator used in the polymerization of Step B described later, using the nitrogen-containing compound X, the metal compound Y, and 1,3-butadiene.
  • the modified conjugated diene is initiated by polymerizing 1,3-butadiene in the presence of a compound obtained by mixing nitrogen-containing compound X and metal compound Y (hereinafter also referred to as “preliminary polymerization”). Prepare the agent.
  • the nitrogen-containing compound X may be either a chain amine compound or a cyclic amine compound.
  • examples of the chain amine compound include a compound represented by the following formula (a-1)
  • examples of the cyclic amine compound include a compound represented by the following formula (a-2).
  • R 4 , R 5 and R 7 are each independently a hydrocarbyl group having 1 to 20 carbon atoms or a trisubstituted hydrocarbylsilyl group.
  • R 6 is having 1 to 12 carbon atoms.
  • R 8 is a hydrocarbylene group having 3 to 16 carbon atoms, or a nitrogen atom, an oxygen atom, a sulfur atom, a phosphorus atom, between the carbon-carbon bonds in the hydrocarbylene group, (It is a divalent group having a specific atom B which is at least one of a silicon atom and a tin atom, and no active hydrogen bonded to the specific atom B.)
  • examples of the hydrocarbyl group having 1 to 20 carbon atoms in R 4 , R 5 and R 7 include, for example, an alkyl group or alkenyl group having 1 to 20 carbon atoms, and an alicyclic group having 3 to 20 carbon atoms. And formula groups and aromatic groups having 6 to 20 carbon atoms.
  • Specific examples thereof include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, n-pentyl group, n-hexyl group, 2-ethylhexyl group, allyl group, A cyclopentyl group, a cyclohexyl group, a phenyl group, a vinyl group, etc. are mentioned.
  • Examples of the trisubstituted hydrocarbylsilyl group of R 4 , R 5 and R 7 include a trimethylsilyl group, a triethylsilyl group, a methyldiethylsilyl group, and a dimethylethylsilyl group.
  • Examples of the hydrocarbylene group having 1 to 12 carbon atoms of R 6 include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a tetramethylene group, and a hexamethylene group.
  • R 6 may be a divalent group having at least one of an oxygen atom, a sulfur atom, and a phosphorus atom between the carbon-carbon bonds in the hydrocarbylene group exemplified above unless it has active hydrogen.
  • active hydrogen refers to a hydrogen atom bonded to an atom other than a carbon atom, and preferably refers to a substance having a bond energy lower than that of polymethylene.
  • examples of the hydrocarbylene group having 3 to 16 carbon atoms of R 8 include trimethylene group, tetramethylene group, hexamethylene group, heptamethylene group, octamethylene group, dodecamethylene group and the like. Can be mentioned.
  • R 8 is a divalent group having at least one of a nitrogen atom, an oxygen atom, a sulfur atom, a phosphorus atom, a silicon atom and a tin atom between the carbon-carbon bonds in the hydrocarbylene group exemplified above. There may be.
  • Specific examples of the compound represented by the formula (a-2) include pyrrolidine, piperidine, hexamethyleneimine, heptamethyleneimine, dodecamethyleneimine, 3-methylpiperidine, 3,3,5-trimethylhexamethyleneimine.
  • the nitrogen-containing compound X is preferably a cyclic amine compound in terms of obtaining a crosslinked rubber that exhibits various properties such as low fuel consumption performance and wet grip properties.
  • a cyclic amine compound is used as the nitrogen-containing compound X, it is presumed that various properties have been improved as described above due to the high polymerization activity of the resulting organometallic amide compound, resulting in a narrow molecular weight distribution.
  • 1 type may be used independently and 2 or more types may be used in combination.
  • metal compound Y examples include methyllithium, ethyllithium, n-propyllithium, n-butyllithium, sec-butyllithium, alkyllithium such as t-butyllithium, 1,4-dilithiobutane, phenyllithium, stilbenelithium, naphthyl.
  • 1,3-butadiene is polymerized to form a butadiene block.
  • a modified conjugated diene initiator having a butadiene block By performing polymerization in the following step B using a modified conjugated diene initiator having a butadiene block, a modified conjugated diene-based polymer improved in a well-balanced processability and hysteresis loss reduction can be obtained.
  • polymerize 1,3-butadiene means that the butadiene block of the modified conjugated diene initiator is a 1,3-butadiene unit as long as the effect of the present disclosure is not impaired. It is allowed to have different structural units.
  • Examples of structural units different from 1,3-butadiene units include conjugated diene units derived from conjugated diene compounds different from 1,3-butadiene, such as isoprene, 2,3-dimethyl-1,3-butadiene. 1,3-pentadiene, 1,3-hexadiene, 1,3-heptadiene, 2-phenyl-1,3-butadiene, 3-methyl-1,3-pentadiene, or 2-chloro-1,3-butadiene Examples are derived structural units.
  • the content ratio of the structural unit different from the 1,3-butadiene unit in the butadiene block of the modified conjugated diene initiator is less than 10% by mass of the total structural units constituting the butadiene block. Is preferably less than 5% by mass, and more preferably less than 1% by mass.
  • the butadiene block contained in the modified conjugated diene initiator is particularly preferably composed of only 1,3-butadiene units from the viewpoint of high fuel economy performance, wear resistance, and wet grip properties.
  • any of solution polymerization method, gas phase polymerization method and bulk polymerization method may be used, but solution polymerization method is particularly preferable.
  • the organic solvent to be used may be any organic solvent inert to the reaction.
  • aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, and the like can be used.
  • hydrocarbons having 3 to 8 carbon atoms are preferable, and specific examples thereof include, for example, propane, n-butane, isobutane, n-pentane, isopentane, n-hexane, cyclohexane, propene, 1-butene and isobutene.
  • the usage ratio of the nitrogen-containing compound X, the metal compound Y, and 1,3-butadiene can be set according to the length of the conjugated diene block of the modified conjugated diene initiator.
  • the use ratio of the metal compound Y is preferably 10 to 2000 mmol, more preferably 50 to 1000 mmol, more preferably 100 to 900 mmol, with respect to 100 g of 1,3-butadiene used for the prepolymerization. More preferably.
  • the use ratio of the nitrogen-containing compound X is preferably 0.1 to 10 mol, more preferably 0.5 to 5 mol, with respect to 1 mol of the metal compound Y.
  • the proportion of 1,3-butadiene used in the prepolymerization is determined in the following step B by using a conjugated diene compound and an aromatic vinyl compound used in the polymerization of a conjugated diene compound and an aromatic vinyl compound using a modified conjugated diene initiator.
  • the total amount is preferably 0.1 to 5% by mass, and more preferably 0.5 to 3% by mass.
  • polymerizing 1,3-butadiene in the presence of a compound obtained by mixing nitrogen-containing compound X and metal compound Y means (1) nitrogen-containing compound X and metal compound Y.
  • the prepolymerization may be performed in the presence of a randomizer for the purpose of adjusting the vinyl bond content representing the vinyl bond content in the conjugated diene block.
  • randomizers include, for example, dimethoxybenzene, tetrahydrofuran, dimethoxyethane, diethylene glycol dibutyl ether, diethylene glycol dimethyl ether, 2,2-di (tetrahydrofuryl) propane, 2- (2-ethoxyethoxy) -2-methylpropane, triethylamine, Examples include pyridine, N-methylmorpholine, and tetramethylethylenediamine. These can be used individually by 1 type or in combination of 2 or more types.
  • the monomer concentration in the reaction solution is preferably 5 to 50% by mass from the viewpoint of maintaining the balance between productivity and ease of polymerization control, and is preferably 10 to 30% by mass. More preferably.
  • the temperature of the polymerization reaction is preferably ⁇ 20 ° C. to 150 ° C., more preferably 0 to 120 ° C.
  • the polymerization reaction is preferably performed under a pressure sufficient to keep the monomer in a substantially liquid phase. Such a pressure can be obtained by a method such as pressurizing the inside of the reactor with a gas inert to the polymerization reaction.
  • Step B the conjugated diene compound and the aromatic vinyl compound are polymerized in the presence of the modified conjugated diene initiator obtained in Step A.
  • a conjugated diene system in which a butadiene block having a nitrogen-containing group at one end is bonded to one end of a copolymer chain having a conjugated diene unit and an aromatic vinyl unit, and the other end is an active end A polymer can be obtained.
  • Examples of the conjugated diene compound used in the polymerization in this step include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, 1,3- Examples include heptadiene, 2-phenyl-1,3-butadiene, 3-methyl-1,3-pentadiene, 2-chloro-1,3-butadiene and the like. Among these, at least one of 1,3-butadiene, isoprene and 2,3-dimethyl-1,3-butadiene is preferable.
  • 1 type may be used independently and 2 or more types may be used in combination.
  • aromatic vinyl compound examples include styrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, ⁇ -methylstyrene, 2,4-dimethylstyrene, 2,4-diisopropylstyrene, and 4-t-butylstyrene.
  • the polymerization in this step is preferably a copolymerization using 1,3-butadiene and styrene, in view of high living property in anionic polymerization.
  • the polymerization of the conjugated diene compound and the aromatic vinyl compound is preferably random polymerization.
  • the proportion of the aromatic vinyl compound used is the sum of the conjugated diene compound and the aromatic vinyl compound used for the polymerization from the viewpoint of improving the balance between the low hysteresis loss property of the vulcanized rubber and the wet grip property.
  • the amount is preferably 3 to 55% by mass, more preferably 5 to 50% by mass.
  • the content ratio of the structural unit derived from the aromatic vinyl compound in the polymer is a value measured by 1 H-NMR.
  • a compound other than the conjugated diene compound and the aromatic vinyl compound may be used as the monomer.
  • other monomers include acrylonitrile, methyl (meth) acrylate, ethyl (meth) acrylate, 1.5-hexadiene, 1,6-heptadiene, and the like.
  • the proportion of other monomers used is preferably 10% by mass or less, and more preferably 5% by mass or less, based on the total amount of monomers used in the polymerization in Step B.
  • any of solution polymerization method, gas phase polymerization method and bulk polymerization method may be used, but the solution polymerization method is particularly preferable.
  • a polymerization form you may use any of a batch type and a continuous type.
  • an example of a specific polymerization method is as follows: a monomer containing a conjugated diene compound and an aromatic vinyl compound in an organic solvent in the presence of a polymerization initiator and a randomizer used as necessary. The method of superposing
  • Step B the modified conjugated diene initiator obtained in Step A is used as a polymerization initiator.
  • the total use ratio of the polymerization initiator can be appropriately set according to the target molecular weight.
  • a modified conjugated diene initiator may use only 1 type and may use it in combination of 2 or more type.
  • the randomizer can be used for the purpose of adjusting the vinyl bond content in the copolymer chain of conjugated diene units and aromatic vinyl units.
  • the description of the process A is applied to a specific example of the randomizer.
  • polymerization should just be an organic solvent inactive to reaction, The compound etc. which were illustrated at the process A as the specific example are mentioned.
  • the description of the preliminary polymerization in Step A is applied.
  • the conjugated diene compound may be added before the polymerization reaction is stopped, and further polymerization may be performed.
  • the copolymer chain of the conjugated diene compound and the aromatic vinyl compound has a butadiene block at the polymerization start terminal, and is formed by polymerizing the conjugated diene compound at the polymerization end terminal.
  • a modified conjugated diene polymer having a conjugated diene block can be obtained.
  • conjugated diene compound to be added examples include compounds exemplified as the conjugated diene compound that may be used in the polymerization in the step B, and among these, low fuel consumption performance, wear resistance, and wet grip properties are improved.
  • 1,3-butadiene is preferred because of its high C ratio.
  • the proportion of the conjugated diene compound used in the addition is preferably 0.1 to 15 g and preferably 1 to 10 g with respect to 1 g of 1,3-butadiene used for preparing the modified conjugated diene initiator. More preferred.
  • the conjugated diene block that may be formed at the polymerization end terminal in the polymerization in Step B is allowed to have a structural unit different from the conjugated diene unit.
  • the content ratio of the structural unit different from the conjugated diene unit in the conjugated diene block is all the structural units constituting the conjugated diene block.
  • the content is preferably less than 5% by mass, more preferably less than 2% by mass, and still more preferably less than 1% by mass.
  • the conjugated diene block that may be formed at the polymerization end terminal in the polymerization in the step B is a butadiene block obtained by polymerizing 1,3-butadiene
  • the content of 1,3-butadiene units in the butadiene block is 80 masses. %, More preferably 90% by mass or more, still more preferably 95% by mass or more, and particularly preferably only 1,3-butadiene units.
  • a modified conjugated diene polymer having a nitrogen-containing group at one end and the active end at the other end can be obtained.
  • the weight-average molecular weight (Mw) in terms of polystyrene determined by gel permeation chromatography (GPC) of the modified conjugated diene polymer having an active end is preferably 5.0 ⁇ 10 4 to 1.0 ⁇ 10 6 .
  • Mw is smaller than 5.0 ⁇ 10 4
  • the tensile strength, low heat build-up and wear resistance of the vulcanized rubber tend to be lowered, and when larger than 1.0 ⁇ 10 6 , the resulting rubber composition
  • the vinyl bond content in the butadiene unit is preferably 30 to 70% by mass, more preferably 33 to 68% by mass, and 35 to 65% by mass. More preferably it is.
  • the vinyl bond content is less than 30% by mass, the grip characteristics tend to be low, and when it exceeds 70% by mass, the wear resistance of the resulting vulcanized rubber tends to decrease.
  • Terminal modification step The modified conjugated diene polymer having an active terminal obtained in Step B may be terminated by using alcohol or the like, but the active terminal of the modified conjugated diene polymer, silica, A compound having an interacting functional group and capable of reacting with the active terminal of the polymer (hereinafter also referred to as “terminal-modified compound”) may be reacted.
  • terminal-modified compound A compound having an interacting functional group and capable of reacting with the active terminal of the polymer
  • the “functional group that interacts with silica” means a group having an element that interacts with silica such as nitrogen, sulfur, phosphorus, and oxygen.
  • “Interaction” refers to an intermolecular force that forms a covalent bond between molecules or is weaker than a covalent bond (eg, ion-dipole interaction, dipole-dipole interaction, hydrogen bond, van der Waals This means that an electromagnetic force between molecules such as force is formed.
  • the terminal-modified compound is preferably a compound having one kind selected from the group consisting of a nitrogen atom, a sulfur atom, a phosphorus atom, an oxygen atom and a silicon atom. Specific examples thereof include, for example, the following compounds (I) to (IV).
  • Compound (B-1) represented by the following formula (1);
  • a 1 has at least one atom selected from the group consisting of a nitrogen atom, a phosphorus atom, and a sulfur atom, does not have active hydrogen, and is a nitrogen atom with respect to R 3 ;
  • a monovalent functional group bonded by a phosphorus atom or a sulfur atom, R 1 and R 2 are hydrocarbyl groups, R 3 is a hydrocarbylene group, and n is an integer of 0 to 2, provided that R 1 When a plurality of 1 and R 2 are present, the plurality of R 1 and R 2 may be the same or different.
  • a functional group P which is at least one selected from the group consisting of a cyclic ether group, a (thio) carbonyl group and an iso (thio) cyanate group, a nitrogen atom, a phosphorus atom, an oxygen atom and sulfur And having at least one atom selected from the group consisting of atoms (provided that at least one of a nitrogen atom, a phosphorus atom and a sulfur atom may be protected by a trisubstituted hydrocarbylsilyl group) and an activity
  • a compound (B-2) having no hydrogen and having at least one group Q different from the functional group P;
  • Compound (B-3) having two or more iso (thio) cyanate groups in the molecule;
  • Compound (B-4) having a silicon-nitrogen bond;
  • these 1 type can be used individually or in combination of 2 or more types.
  • the (thio) carbonyl group represents a carbonyl group and a thiocarbonyl group
  • the iso (thio) cyanate group represents an isocyanate group and an isothiocyanate group.
  • the hydrocarbyl group of R 1 and R 2 is a linear or branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, or an aryl having 6 to 20 carbon atoms. It is preferably a group.
  • R 3 is preferably a linear or branched alkanediyl group having 1 to 20 carbon atoms, a cycloalkylene group having 3 to 20 carbon atoms, or an arylene group having 6 to 20 carbon atoms.
  • n is preferably 0 or 1 from the viewpoint of increasing the reactivity with the conjugated diene polymer.
  • a 1 has at least one atom selected from the group consisting of a nitrogen atom, a phosphorus atom and a sulfur atom (hereinafter also referred to as a specific atom C), and is bonded to R 3 with the specific atom C.
  • the specific atom C is not bonded to active hydrogen and may be protected with a protecting group.
  • the “protecting group” is a functional group that converts A 1 into a functional group that is inactive with respect to the polymerization active terminal, and examples thereof include a trisubstituted hydrocarbylsilyl group.
  • a 1 is preferably a group capable of becoming an onium ion by the onium salt generator.
  • the compound (B-1) include a nitrogen-containing group in which two hydrogen atoms of a primary amino group are substituted by two protecting groups, and one hydrogen atom of a secondary amino group is substituted by one protecting group.
  • the compound having a substituted nitrogen-containing group or tertiary amino group and an alkoxysilyl group include N, N-bis (trimethylsilyl) aminopropyltrimethoxysilane and N, N-bis (trimethylsilyl) aminopropylmethyl.
  • Examples of the compound having a group having a carbon-nitrogen double bond or a nitrogen-containing heterocyclic group and an alkoxysilyl group include N- (1,3-dimethylbutylidene) -3- (triethoxysilyl) -1 -Propanamine, N- (1-methylpropylidene) -3- (triethoxysilyl) -1-propanamine, N- (4-N, N-dimethylaminobenzylidene) -3- (triethoxysilyl) -1 -Propanamine, N- (cyclohexylidene) -3- (triethoxysilyl) -1-propanamine, N- (3-trimethoxysilylpropyl) -4,5-dihydroimidazole, N- (3-trimethoxy Silylpropyl) imidazole, 3-hexamethyleneiminopropyltrimethoxysilane, 3-hexamethyleneiminopropylmethyldime
  • a phosphorus-containing group in which two hydrogen atoms of a primary phosphino group are substituted by two protecting groups a phosphorus-containing group in which one hydrogen atom of a secondary phosphino group is substituted by one protecting group, a tertiary phosphino group
  • a compound having a sulfur-containing group in which one hydrogen atom of a thiol group is substituted with one protecting group and an alkoxysilyl group for example, P, P-bis (trimethylsilyl) phosphinopropylmethyldimethoxysilane , P, P-bis (trimethylsilyl) phosphinopropyltrimethoxysilane, 3-dimethylphosphinopropyltrimethoxysilane, 3-dimethylphosphinopropylmethyldimethoxysilane, 3-diphenylphosphinopropyltrimethoxysilane, 3-diphenylphosphinopropyltrimethoxy
  • Examples include compounds substituted with alkanediyl groups.
  • Examples of the compound having an iso (thio) cyanate group include 3-isocyanatopropyltrimethoxysilane and 3-isocyanatopropyltriethoxysilane.
  • the group Q is preferably a group containing a nitrogen atom not bonded to active hydrogen.
  • the compound (B-2) in this case include, as a compound having a cyclic ether group, for example, an epoxyamine compound such as tetraglycidyl-1,3-bisaminomethylcyclohexane and the like;
  • compounds having a (thio) carbonyl group include 4-aminoacetophenone such as 4-N, N-dimethylaminobenzophenone; bis (dihydrocarbylaminoalkyl) such as 1,7-bis (methylethylamino) -4-heptanone Ketone: dihydrocarbylaminoalkyl (meth) acrylate such as 2-dimethylaminoethyl acrylate; Hydrocarbyl imidazolidinone such as 1,3-dimethyl-2-imidazolidinone; N-hydrocarbyl pyrrolidone such as 1-pheny
  • Examples of the compound (B-3) include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate, triphenylmethane triisocyanate, p-phenylene diisocyanate. Narate, tris (isocyanatophenyl) thiophosphate, xylene diisocyanate, benzene-1,2,4-triisocyanate, naphthalene-1,2,5,7-tetraisocyanate, 1,4-phenylenediisothiocyanate Narts can be mentioned.
  • the compound (B-4) include 2- (2,2-dimethoxy-1,2-azasilolidin-1-yl) -N, N-diethylethane-1-amine, 2- (2,2 -Dimethoxy-1,2-azasilolidin-1-yl) -N, N-dimethylethane-1-amine, 3- (2,2-dimethoxy-1,2-azasilolidin-1-yl) -N, N-diethyl Propan-1-amine, 2- (2,2-dimethoxy-1-aza-2-silacyclohexane-1-yl) -N, N-diethylethane-1-amine, 2,2-dimethoxy-1-phenyl- 1,2-azasilolidine, Nn-butyl-aza-2,2-dialkoxysilacyclopentane, 2,2-dimethoxy-1- (3-trimethoxysilylpropyl) -1-aza-2-silacyclopentane , 2, 2 Diethoxy-1- (3
  • the terminally modified compound it is particularly preferable to use at least one selected from the group consisting of the compound (B-1) and the compound (B-4) in view of strong affinity with silica, and the compound (B-1) It is more preferable to use
  • the compound (B-1) is used, for the purpose of adjusting the Mooney viscosity of the modified conjugated diene polymer, together with the compound (B-1), silicon tetrachloride, a polyfunctional epoxy compound (for example, tetraglycidyl- A coupling agent such as 1,3-bisaminomethylcyclohexane may be used in combination.
  • the modification reaction with the terminal modification compound can be performed, for example, as a solution reaction.
  • This solution reaction may be carried out using a solution containing unreacted monomers after the completion of the polymerization reaction.
  • the conjugated diene polymer contained in the solution is isolated and dissolved in a suitable solvent such as cyclohexane. You may go.
  • the denaturation reaction may be performed using either a batch system or a continuous system.
  • the method for adding the terminal-modified compound is not particularly limited, and examples thereof include a method of adding all at once, a method of adding in divided portions, and a method of adding continuously.
  • the amount of the terminal-modified compound to be used may be appropriately set according to the kind of the compound to be used for the reaction, but is preferably 0.1 with respect to the metal atom involved in the polymerization reaction of the polymerization initiator.
  • Molar equivalent or more more preferably 0.3 molar equivalent or more.
  • the temperature of the modification reaction is usually the same as the temperature of the polymerization reaction, preferably ⁇ 20 ° C. to 150 ° C., more preferably 0 to 120 ° C., and particularly preferably 20 to 100 ° C. .
  • the reaction time of the denaturation reaction is preferably 1 minute to 5 hours, more preferably 2 minutes to 1 hour. Isolation of the conjugated diene polymer contained in the reaction solution can be carried out by a known solvent removal method such as steam stripping and a drying operation such as heat treatment.
  • the modified conjugated diene polymer having an active end may be reacted with a coupling agent to inactivate the active end of the modified conjugated diene polymer chain to adjust the molecular weight.
  • a coupling agent conventionally known coupling agents can be used.
  • the reaction between the polymerization active terminal and the coupling agent can be performed, for example, as a solution reaction.
  • the amount of the coupling agent used is preferably at least 0.1 molar equivalent, more preferably at least 0.3 molar equivalent, relative to the metal atom involved in the polymerization reaction of the polymerization initiator.
  • the description of the terminal modification step is applied to various conditions such as reaction type, reaction temperature, and reaction time.
  • a conjugated diene block is bonded to each of both ends of a copolymer chain having a conjugated diene unit and an aromatic vinyl unit.
  • one conjugated diene block is a butadiene block formed by polymerizing 1,3-butadiene, and a nitrogen-containing group at the terminal of the butadiene block that is not bonded to the copolymer chain.
  • the other conjugated diene block is a polymer having a functional group that interacts with silica at the terminal not bonded to the copolymer chain.
  • the resulting vulcanized rubber is preferable because it has a high effect of improving fuel efficiency, wear resistance, and wet grip properties.
  • the polymer may be linear or branched.
  • the polymer composition of the present disclosure contains a rubber component including the modified conjugated diene polymer, an inorganic filler, and a crosslinking agent.
  • the content ratio of the modified conjugated diene polymer in the polymer composition is preferably 20% by mass or more of the rubber component contained in the polymer composition, and more preferably 30% by mass or more. Preferably, it is more preferably 40% by mass or more.
  • at least one of silica and carbon black can be preferably used as the inorganic filler.
  • silica examples include wet silica (hydrous silicic acid), dry silica (anhydrous silicic acid), colloidal silica, precipitated silica, calcium silicate, and aluminum silicate.
  • wet silica is particularly preferable from the viewpoint of the effect of improving fracture characteristics and the effect of achieving both wet grip properties and low rolling resistance.
  • high dispersible type silica from the viewpoint of improving dispersibility in the polymer composition and improving physical properties and processability.
  • a silica can be used individually by 1 type or in combination of 2 or more types.
  • carbon black examples include GPF, FEF, HAF, ISAF, and SAF, but are not particularly limited. By using carbon black as the inorganic filler, a good reinforcing effect can be obtained.
  • various reinforcing fillers such as clay and calcium carbonate may be blended as a filler in addition to silica and carbon black.
  • the total amount of silica and carbon black in the polymer composition is preferably 20 to 130 parts by mass, more preferably 25 to 110 parts by mass with respect to 100 parts by mass of the total amount of the polymer components contained in the polymer composition. Part.
  • crosslinking agent examples include sulfur, sulfur halides, organic peroxides, quinonedioximes, organic polyvalent amine compounds, alkylphenol resins having a methylol group, and sulfur is usually used.
  • the amount of sulfur is preferably 0.1 to 5 parts by mass, more preferably 0.5 to 3 parts by mass with respect to 100 parts by mass of the total amount of polymer components contained in the polymer composition.
  • Another rubber component different from the modified conjugated diene polymer obtained above may be further blended in the polymer composition of the present disclosure.
  • the type of the other rubber component is not particularly limited, but butadiene rubber (BR, such as high cis BR having 90% or more of cis-1,4 bond, BR containing syndiotactic-1,2-polybutadiene (SPB), etc.), styrene Examples thereof include butadiene rubber (SBR), natural rubber (NR), isoprene rubber (IR), styrene isoprene copolymer rubber, and butadiene isoprene copolymer rubber.
  • BR butadiene rubber
  • NR natural rubber
  • IR isoprene rubber
  • styrene isoprene copolymer rubber and butadiene isoprene copolymer rubber.
  • the other rubber component is at least selected from the group consisting of modified and unmodified BR and SBR in that the effect of reducing hysteresis loss and improving wear resistance is high by using the modified conjugated diene polymer of the present disclosure. It is preferable that it is 1 type, and it is preferable that it is NR at the point that the improvement effect of wet grip property and workability is high.
  • the blending amount of the other rubber components is preferably 5 to 60 parts by mass, more preferably 10 to 50 parts by mass with respect to 100 parts by mass of the total amount of the polymer components contained in the polymer composition.
  • the polymer composition includes, for example, anti-aging agent, zinc white, stearic acid, softener, sulfur, vulcanization accelerator, silane coupling agent, compatibilizer, vulcanization aid, process
  • Various additives generally used in tire rubber compositions such as oil, processing aids, and scorch inhibitors can be blended. These blending ratios can be appropriately selected according to various components within a range not impairing the effects of the present disclosure.
  • the components to be blended as necessary include an open kneader (for example, a roll) and a closed kneader (for example, a Banbury mixer). Etc.) and can be applied to various rubber products as a crosslinked product by crosslinking (vulcanizing) after molding.
  • an open kneader for example, a roll
  • a closed kneader for example, a Banbury mixer
  • tire applications such as tire treads, under treads, carcass, sidewalls, and bead parts; seal materials such as packings, gaskets, weather strips, O-rings; various vehicles such as automobiles, ships, aircraft, and railways Interior and exterior skin materials for building; building materials; anti-vibration rubber for industrial machinery and equipment; various hoses and hose covers such as diaphragms, rolls, radiator hoses and air hoses; belts such as power transmission belts; Dust boots; Medical equipment materials; Fenders; Wire insulation materials; Other industrial products.
  • seal materials such as packings, gaskets, weather strips, O-rings
  • various vehicles such as automobiles, ships, aircraft, and railways Interior and exterior skin materials for building; building materials; anti-vibration rubber for industrial machinery and equipment
  • various hoses and hose covers such as diaphragms, rolls, radiator hoses and air hoses
  • belts such as power transmission belts; Dust boots; Medical equipment materials; Fenders; Wire insulation materials;
  • a modified conjugated diene polymer is produced that is capable of obtaining a vulcanized rubber that is excellent in processability of the rubber composition and that is excellent in low fuel consumption performance, wear resistance, and wet grip characteristics. can do. Therefore, the polymer composition containing the modified conjugated diene polymer of the present disclosure can be suitably used particularly as a material for tire treads and sidewalls.
  • Tire production can be performed according to conventional methods. For example, a polymer composition is mixed in a kneader and formed into a sheet shape, and then placed at a predetermined position according to a conventional method and vulcanized to form a tread rubber or a sidewall rubber, thereby obtaining a pneumatic tire. It is done.
  • Example 1-1 Synthesis of modified conjugated diene rubber B
  • An autoclave reactor with an internal volume of 5 liters purged with nitrogen was charged with 2450 g of cyclohexane, 3.37 mmol of 2,2-di (2-tetrahydrofuryl) propane, 170 g of styrene and 422 g of 1,3-butadiene.
  • the polymerization was carried out under adiabatic conditions and the maximum temperature reached 85 ° C.
  • the modified conjugated diene rubber B was obtained by drying with a heated hot roll.
  • the polymerization formulation of the modified conjugated diene rubber B is shown in Table 1 below, and the properties of the resulting modified conjugated diene rubber B are shown in Table 2 below.
  • Example 1-2 and 1-3 The type of polymerization initiator used was changed to Example 1-1, except that Example 1-2 was changed to modified conjugated diene initiator B, and Example 1-3 was changed to modified conjugated diene initiator C.
  • Modified conjugated diene rubbers C and D were obtained in the same manner as described above (see Table 1 below).
  • the blending amount of the modified conjugated diene initiator B and the modified conjugated diene initiator C was set to 7 mmol of lithium as in Example 1-1.
  • the properties of the resulting modified conjugated diene rubbers C and D are shown in Table 2 below.
  • the numerical values of the modified conjugated diene initiators A to C represent the amount (mmol) of lithium that each initiator has.
  • the modified conjugated diene initiators A to C are indicated as “initiators A to C”, respectively.
  • Abbreviations of the compounds are as follows. DTHP (* 1); 2,2-di (2-tetrahydrofuryl) propane INI-N-2 (* 2); N- (tert-butyldimethylsilyl) piperazine INI-N-3 (* 3); piperidine N -Si-1 (* 4); N, N-bis (trimethylsilyl) aminopropylmethyldiethoxysilane BHT (* 5); 2,6-di-tert-butyl-4-methyl-phenol
  • Example 2-1 Preparation of rubber composition and evaluation of physical properties
  • the rubber composition prepared according to the formulation shown in Table 3 below was vulcanized to evaluate the physical properties.
  • the kneading method and evaluation method of the rubber composition are as follows. ⁇ Kneading method and evaluation method of rubber composition Using a plastmill (with an internal volume of 250 cc) equipped with a temperature control device, as a first-stage kneading, under conditions of a filling rate of 72% and a rotational speed of 60 rpm, a rubber component, silica Carbon black, silane coupling agent, stearic acid, anti-aging agent, and zinc oxide were kneaded.
  • Example 2-1 70 parts by mass of modified conjugated diene rubber B and 30 parts by mass of butadiene rubber (BR01, manufactured by JSR Corporation) were used as rubber components (see Table 4 below).
  • BR01 butadiene rubber
  • the blend obtained above was cooled to room temperature, and then sulfur and a vulcanization accelerator were added and kneaded. This was molded and vulcanized with a vulcanizing press at 160 ° C. for a predetermined time, and the characteristic evaluation representing the following tire performance was performed.
  • Example 2-2 to 2-6 Comparative Examples 2-1 to 2-6
  • a rubber composition was prepared in the same manner as in Example 2-1, except that the types and amounts of the rubber components used were changed as shown in Table 4 below, and the prepared rubber composition was vulcanized to evaluate physical properties. went. The results of physical property evaluation are shown in Tables 5 and 6 below.
  • the modified conjugated diene rubbers obtained in Examples 2-1 to 2-6 are more processed than the modified conjugated diene rubbers obtained in Comparative Examples. And the low fuel consumption performance, wear resistance, and wet grip properties of the vulcanized rubber were balanced.
  • Examples 2-1 and 2-4 using BR as other rubber among the rubber components have improved hysteresis loss and abrasion resistance widths than Examples 2-3 and 2-6 using NR. Largely, Examples 2-3 and 2-6 using NR had a greater improvement in wet grip characteristics than Examples 2-1 and 2-4 using BR.
  • the rubber composition is excellent in processability and has low fuel consumption performance, wear resistance and wet grip characteristics. It was confirmed that an excellent vulcanized rubber can be obtained.

Abstract

This modified conjugate diene-based polymer is produced by a production method that comprises: step A for polymerizing 1,3-butadiene in the presence of a compound obtained by mixing a nitrogen-containing compound X having a nitrogen atom to which a hydrogen atom is bonded and a metal compound Y being an alkali metal compound and/or an alkali earth metal compound; and step B for polymerizing a conjugate compound and an aromatic vinyl compound in the presence of the polymer obtained in step A.

Description

変性共役ジエン系重合体の製造方法、変性共役ジエン系重合体、重合体組成物、架橋物及びタイヤMethod for producing modified conjugated diene polymer, modified conjugated diene polymer, polymer composition, crosslinked product and tire 関連出願の相互参照Cross-reference of related applications
　本出願は、２０１６年１１月１６日に出願された日本出願番号２０１６－２２３５８１号に基づくもので、ここにその記載内容を援用する。 This application is based on Japanese Patent Application No. 2016-223581 filed on November 16, 2016, the contents of which are incorporated herein by reference.
　本開示は、変性共役ジエン系重合体の製造方法、変性共役ジエン系重合体、重合体組成物、架橋物及びタイヤに関するものである。 The present disclosure relates to a method for producing a modified conjugated diene polymer, a modified conjugated diene polymer, a polymer composition, a crosslinked product, and a tire.
　共役ジエン化合物を用いた重合により得られる共役ジエン系重合体は、耐熱性、耐摩耗性、機械的強度、成形加工性等の各種特性が良好であることから、空気入りタイヤや防振ゴム、ホースなどの各種工業製品に広く使用されている。 A conjugated diene polymer obtained by polymerization using a conjugated diene compound has good properties such as heat resistance, wear resistance, mechanical strength, and moldability, so that a pneumatic tire, a vibration-proof rubber, Widely used in various industrial products such as hoses.
　空気入りタイヤとしては、低燃費性能に優れていることが要求される。こうした要求に応えるべく、従来、共役ジエン系重合体鎖の重合開始末端や終了末端にシリカと相互作用する官能基を導入した変性共役ジエン系重合体が種々提案されている（例えば、特許文献１や特許文献２参照）。末端変性した共役ジエン系重合体は、未変性の共役ジエン系重合体に比べて、カーボンブラックやシリカ等の補強剤としてのフィラーとの相性が良いことから、発熱を抑えて低燃費性能を向上させることが可能となる。 ¡Pneumatic tires are required to have excellent fuel efficiency. In order to meet such demands, various modified conjugated diene polymers in which functional groups that interact with silica are introduced at the polymerization initiation terminal and termination terminal of a conjugated diene polymer chain have been proposed (for example, Patent Document 1). And Patent Document 2). End-modified conjugated diene polymers have better compatibility with fillers as reinforcing agents such as carbon black and silica compared to unmodified conjugated diene polymers, thus reducing heat generation and improving fuel efficiency. It becomes possible to make it.
　また従来、タイヤ用途に用いる共役ジエン系ゴムとして、少なくとも一方の末端がイソプレン単量体単位を７０質量％以上有するイソプレンブロックであり、他方の末端が活性末端である共役ジエン系重合体鎖と、特定の変性剤とを反応させて得られる共役ジエン系ゴムが提案されている（例えば、特許文献３，４参照）。 Conventionally, as a conjugated diene rubber used for tire use, at least one end is an isoprene block having 70% by mass or more of isoprene monomer units, and the other end is a conjugated diene polymer chain having an active end; Conjugated diene rubbers obtained by reacting with specific modifiers have been proposed (see, for example, Patent Documents 3 and 4).
特開２００３－１７１４１８号公報JP 2003-171418 A 国際公開第２０１３／９４６２９号International Publication No. 2013/94629 国際公開第２０１１／１０５３６２号International Publication No. 2011/105362 国際公開第２０１２／８６４９６号International Publication No. 2012/86496
　昨今における二酸化炭素の排出による地球温暖化等の環境事情や、省資源・省エネルギーに対する意識の向上、ガソリンの価格高騰等の経済事情などにより、自動車タイヤ用ゴムとしては、従来よりも増して低燃費性能に優れた材料が望まれている。また近年では、電気自動車の普及が進んでいるが、電気自動車においては電池の搭載により車両重量が従来よりも重く、航続距離の拡大やタイヤの摩耗低減の重要性が増している。このように、自動車タイヤ用ゴムにおいては、低燃費性能とともに、耐摩耗性や加工性、ウェットグリップ特性などの各種タイヤ特性についてもバランス良く優れていることが求められる。 Due to recent environmental issues such as global warming due to carbon dioxide emissions, increased awareness of resource and energy savings, and economic circumstances such as rising gasoline prices, automobile tire rubber is more fuel-efficient than ever. Materials with excellent performance are desired. In recent years, electric vehicles have been widely used. However, electric vehicles are heavier than conventional vehicles due to the installation of batteries, and the importance of increasing the cruising range and reducing tire wear is increasing. As described above, the rubber for automobile tires is required to be excellent in a balanced manner with respect to various tire characteristics such as wear resistance, workability, and wet grip characteristics as well as low fuel consumption performance.
　本開示は上記課題に鑑みなされたものであり、ゴム組成物の加工性に優れ、かつ低燃費性能、耐摩耗性及びウェットグリップ特性に優れた加硫ゴムを得ることができる変性共役ジエン系重合体を提供することを一つの目的とする。 The present disclosure has been made in view of the above problems, and is a modified conjugated diene-based heavy polymer that can provide a vulcanized rubber that is excellent in processability of the rubber composition and that is excellent in low fuel consumption performance, wear resistance, and wet grip characteristics. One purpose is to provide coalescence.
　上記課題を解決すべく、本開示によれば、以下の変性共役ジエン系重合体の製造方法、変性共役ジエン系重合体、重合体組成物、架橋物及びタイヤが提供される。 In order to solve the above problems, according to the present disclosure, the following modified conjugated diene polymer production method, modified conjugated diene polymer, polymer composition, cross-linked product and tire are provided.
　［１］　水素原子が結合した窒素原子を有する窒素含有化合物Ｘと、アルカリ金属化合物及びアルカリ土類金属化合物の少なくともいずれかの金属化合物Ｙとを混合して得られる化合物の存在下で１，３－ブタジエンを重合する工程Ａと、前記工程Ａで得られた重合体の存在下で、共役ジエン化合物及び芳香族ビニル化合物を含むモノマーを重合する工程Ｂと、を含む変性共役ジエン系重合体の製造方法。
　［２］　共役ジエン単位と芳香族ビニル単位とを有する共重合体鎖の両末端に、共役ジエン化合物を重合して形成された共役ジエンブロックがそれぞれ結合されており、かつ、一方の前記共役ジエンブロックが、１，３－ブタジエンを重合して形成されたブタジエンブロックであり、前記共重合体鎖に結合していない側の末端に窒素含有基を有し、他方の前記共役ジエンブロックが、前記共重合体鎖に結合していない側の末端にシリカと相互作用する官能基を有する、変性共役ジエン系重合体。
　［３］　１，３－ブタジエンを重合して形成された共役ジエンブロックの一方の末端に窒素含有基を有し、他方の末端が活性末端である重合体鎖の存在下で、共役ジエン化合物及び芳香族ビニル化合物を重合して得られる変性共役ジエン系重合体。
　［４］　上記［１］の製造方法により得られる変性共役ジエン系重合体、又は上記［２］若しくは［３］の変性共役ジエン系重合体と、無機フィラーと、架橋剤とを含む重合体組成物。
　［５］　上記［４］の重合体組成物を架橋させてなる架橋物。
　［６］　上記［５］の架橋物を用いて形成されたタイヤ。 [1] 1,3 in the presence of a compound obtained by mixing a nitrogen-containing compound X having a nitrogen atom to which a hydrogen atom is bonded and a metal compound Y of at least one of an alkali metal compound and an alkaline earth metal compound -A modified conjugated diene polymer comprising a step A for polymerizing butadiene and a step B for polymerizing a monomer containing a conjugated diene compound and an aromatic vinyl compound in the presence of the polymer obtained in the step A. Production method.
[2] A conjugated diene block formed by polymerizing a conjugated diene compound is bonded to both ends of a copolymer chain having a conjugated diene unit and an aromatic vinyl unit, and one of the conjugated dienes The block is a butadiene block formed by polymerizing 1,3-butadiene, has a nitrogen-containing group at the terminal not bonded to the copolymer chain, and the other conjugated diene block is A modified conjugated diene polymer having a functional group that interacts with silica at a terminal not bonded to a copolymer chain.
[3] In the presence of a polymer chain having a nitrogen-containing group at one end of a conjugated diene block formed by polymerizing 1,3-butadiene and the other end being an active end, A modified conjugated diene polymer obtained by polymerizing an aromatic vinyl compound.
[4] A polymer composition comprising the modified conjugated diene polymer obtained by the production method of [1], or the modified conjugated diene polymer of [2] or [3], an inorganic filler, and a crosslinking agent. object.
[5] A crosslinked product obtained by crosslinking the polymer composition of [4].
[6] A tire formed using the cross-linked product of [5].
　本開示によれば、ゴム組成物の加工性に優れ、しかも低燃費性能、耐摩耗性及びウェットグリップ特性に優れた加硫ゴムが得られる変性共役ジエン系重合体を得ることができる。 According to the present disclosure, it is possible to obtain a modified conjugated diene polymer that provides a vulcanized rubber that is excellent in processability of the rubber composition and that is excellent in low fuel consumption performance, wear resistance, and wet grip characteristics.
　本開示の変性共役ジエン系重合体は、重合開始剤として、１，３－ブタジエンを重合して形成された重合体鎖（以下、「ブタジエンブロック」ともいう。）の一方の末端に窒素含有基を有し、他方の末端が活性末端である変性共役ジエン開始剤を用いた重合により得られる。当該変性共役ジエン系重合体は、以下の工程Ａ及び工程Ｂを含む方法により製造することができる。以下、本開示の態様に関連する事項について詳細に説明する。 The modified conjugated diene polymer of the present disclosure has a nitrogen-containing group at one end of a polymer chain formed by polymerizing 1,3-butadiene as a polymerization initiator (hereinafter also referred to as “butadiene block”). And is obtained by polymerization using a modified conjugated diene initiator having the other end as an active end. The modified conjugated diene polymer can be produced by a method including the following step A and step B. Hereinafter, matters related to aspects of the present disclosure will be described in detail.
＜工程Ａ＞
　本工程は、窒素含有化合物Ｘと金属化合物Ｙと１，３－ブタジエンとを用いて、後述する工程Ｂの重合で使用する重合開始剤である変性共役ジエン開始剤を調製する工程である。具体的には、窒素含有化合物Ｘと金属化合物Ｙとを混合して得られる化合物の存在下で１，３－ブタジエンを重合（以下、「予備重合」ともいう。）することにより変性共役ジエン開始剤を調製する。 <Process A>
This step is a step of preparing a modified conjugated diene initiator, which is a polymerization initiator used in the polymerization of Step B described later, using the nitrogen-containing compound X, the metal compound Y, and 1,3-butadiene. Specifically, the modified conjugated diene is initiated by polymerizing 1,3-butadiene in the presence of a compound obtained by mixing nitrogen-containing compound X and metal compound Y (hereinafter also referred to as “preliminary polymerization”). Prepare the agent.
　窒素含有化合物Ｘとしては、第２級アミン化合物を好ましく用いることができる。窒素含有化合物Ｘは、鎖状アミン化合物及び環状アミン化合物のいずれであってもよい。具体的には、鎖状アミン化合物として、例えば下記式（ａ－１）で表される化合物が挙げられ、環状アミン化合物として、例えば下記式（ａ－２）で表される化合物が挙げられる。
Figure JPOXMLDOC01-appb-C000001
 （式（ａ－１）中、Ｒ４、Ｒ５及びＲ７は、それぞれ独立に、炭素数１～２０のヒドロカルビル基又は３置換のヒドロカルビルシリル基である。Ｒ６は、炭素数１～１２のヒドロカルビレン基、又は当該ヒドロカルビレン基における炭素－炭素結合間に、酸素原子、硫黄原子及びリン原子の少なくともいずれかである特定原子Ａを有し、かつ特定原子Ａに活性水素が結合していない２価の基である。ｉは０又は１である。）
Figure JPOXMLDOC01-appb-C000002
 （式（ａ－２）中、Ｒ８は、炭素数３～１６のヒドロカルビレン基、又は当該ヒドロカルビレン基における炭素－炭素結合間に、窒素原子、酸素原子、硫黄原子、リン原子、ケイ素原子及びスズ原子の少なくともいずれかである特定原子Ｂを有し、かつ特定原子Ｂに活性水素が結合していない２価の基である。） As the nitrogen-containing compound X, a secondary amine compound can be preferably used. The nitrogen-containing compound X may be either a chain amine compound or a cyclic amine compound. Specifically, examples of the chain amine compound include a compound represented by the following formula (a-1), and examples of the cyclic amine compound include a compound represented by the following formula (a-2).
Figure JPOXMLDOC01-appb-C000001
 (In formula (a-1), R 4 , R 5 and R 7 are each independently a hydrocarbyl group having 1 to 20 carbon atoms or a trisubstituted hydrocarbylsilyl group. R 6 is having 1 to 12 carbon atoms. Or a specific atom A which is at least one of an oxygen atom, a sulfur atom and a phosphorus atom, and an active hydrogen is bonded to the specific atom A between the carbon-carbon bonds of the hydrocarbylene group (I is 0 or 1).
Figure JPOXMLDOC01-appb-C000002
 (In the formula (a-2), R 8 is a hydrocarbylene group having 3 to 16 carbon atoms, or a nitrogen atom, an oxygen atom, a sulfur atom, a phosphorus atom, between the carbon-carbon bonds in the hydrocarbylene group, (It is a divalent group having a specific atom B which is at least one of a silicon atom and a tin atom, and no active hydrogen bonded to the specific atom B.)
　上記式（ａ－１）において、Ｒ４、Ｒ５及びＲ７における炭素数１～２０のヒドロカルビル基としては、例えば炭素数１～２０のアルキル基又はアルケニル基、炭素数３～２０の脂環式基、炭素数６～２０の芳香族基などを挙げることができる。これらの具体例としては、例えばメチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、ｔ－ブチル基、ｎ－ペンチル基、ｎ－ヘキシル基、２－エチルヘキシル基、アリル基、シクロペンチル基、シクロヘキシル基、フェニル基、ビニル基などが挙げられる。
　Ｒ４、Ｒ５及びＲ７の３置換のヒドロカルビルシリル基としては、例えばトリメチルシリル基、トリエチルシリル基、メチルジエチルシリル基、ジメチルエチルシリル基などが挙げられる。 In the above formula (a-1), examples of the hydrocarbyl group having 1 to 20 carbon atoms in R 4 , R 5 and R 7 include, for example, an alkyl group or alkenyl group having 1 to 20 carbon atoms, and an alicyclic group having 3 to 20 carbon atoms. And formula groups and aromatic groups having 6 to 20 carbon atoms. Specific examples thereof include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, n-pentyl group, n-hexyl group, 2-ethylhexyl group, allyl group, A cyclopentyl group, a cyclohexyl group, a phenyl group, a vinyl group, etc. are mentioned.
Examples of the trisubstituted hydrocarbylsilyl group of R 4 , R 5 and R 7 include a trimethylsilyl group, a triethylsilyl group, a methyldiethylsilyl group, and a dimethylethylsilyl group.
　Ｒ６の炭素数１～１２のヒドロカルビレン基としては、例えばメチレン基、エチレン基、トリメチレン基、テトラメチレン基、テトラメチレン基、ヘキサメチレン基等が挙げられる。Ｒ６は、活性水素を有さない限り、上記例示したヒドロカルビレン基における炭素－炭素結合間に、酸素原子、硫黄原子及びリン原子のうち少なくともいずれかを有する２価の基であってもよい。なお、本明細書において、「活性水素」とは、炭素原子以外の原子に結合した水素原子をいい、好ましくはポリメチレンの炭素－水素結合よりも結合エネルギーが低いものを指す。 Examples of the hydrocarbylene group having 1 to 12 carbon atoms of R 6 include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a tetramethylene group, and a hexamethylene group. R 6 may be a divalent group having at least one of an oxygen atom, a sulfur atom, and a phosphorus atom between the carbon-carbon bonds in the hydrocarbylene group exemplified above unless it has active hydrogen. Good. In the present specification, “active hydrogen” refers to a hydrogen atom bonded to an atom other than a carbon atom, and preferably refers to a substance having a bond energy lower than that of polymethylene.
　上記式（ａ－１）で表される化合物の具体例としては、ｉ＝０である場合として、例えばジメチルアミン、ジエチルアミン、ジプロピルアミン、ジブチルアミン、ジシクロヘキシルアミン、Ｎ－メチルベンジルアミン、ジ－（２－エチルヘキシル）アミン、ジアリルアミン、ビス（トリメチルシリル）アミン等を；ｉ＝１である場合として、例えばＮ，Ｎ’－ジメチル－Ｎ’－トリメチルシリル－１，６－ジアミノエタン、Ｎ，Ｎ’－ジメチル－Ｎ’－トリメチルシリル－１，６－ジアミノブタン、Ｎ，Ｎ’－ジメチル－Ｎ’－トリメチルシリル－１，６－ジアミノペンタン、Ｎ，Ｎ’－ジメチル－Ｎ’－トリメチルシリル－１，６－ジアミノヘキサン等を挙げることができる。 Specific examples of the compound represented by the above formula (a-1) include the case where i = 0, for example, dimethylamine, diethylamine, dipropylamine, dibutylamine, dicyclohexylamine, N-methylbenzylamine, di- (2-ethylhexyl) amine, diallylamine, bis (trimethylsilyl) amine, etc .; where i = 1, for example, N, N′-dimethyl-N′-trimethylsilyl-1,6-diaminoethane, N, N′— Dimethyl-N'-trimethylsilyl-1,6-diaminobutane, N, N'-dimethyl-N'-trimethylsilyl-1,6-diaminopentane, N, N'-dimethyl-N'-trimethylsilyl-1,6-diamino Examples include hexane.
　上記式（ａ－２）において、Ｒ８の炭素数３～１６のヒドロカルビレン基としては、例えばトリメチレン基、テトラメチレン基、ヘキサメチレン基、ヘプタメチレン基、オクタメチレン基、ドデカメチレン基などが挙げられる。また、Ｒ８は、上記例示したヒドロカルビレン基における炭素－炭素結合間に、窒素原子、酸素原子、硫黄原子、リン原子、ケイ素原子及びスズ原子のうち少なくともいずれかを有する２価の基であってもよい。 In the above formula (a-2), examples of the hydrocarbylene group having 3 to 16 carbon atoms of R 8 include trimethylene group, tetramethylene group, hexamethylene group, heptamethylene group, octamethylene group, dodecamethylene group and the like. Can be mentioned. R 8 is a divalent group having at least one of a nitrogen atom, an oxygen atom, a sulfur atom, a phosphorus atom, a silicon atom and a tin atom between the carbon-carbon bonds in the hydrocarbylene group exemplified above. There may be.
　上記式（ａ－２）で表される化合物の具体例としては、例えばピロリジン、ピペリジン、ヘキサメチレンイミン、ヘプタメチレンイミン、ドデカメチレンイミン、３－メチルピペリジン、３，３，５－トリメチルヘキサメチレンイミン、ヘキサデカメチレンイミン、２－（２－エチルヘキシル）ピロリジン、３，５－ビス（２－エチルヘキシル）ピペリジン、４－フェニルピペリジン、モルホリン等といった、窒素原子を１個有する化合物；４－プロピルピペラジン、Ｎ－トリメチルシリルピペラジン、Ｎ－（ｔｅｒｔ－ブチルジメチルシリル）ピペラジン等といった、窒素原子を２個有する化合物；１，３－ジトリメチルシリル－１，３，５－トリアジナン等といった、窒素原子を３個有する化合物；１，３，３－トリメチル－６－アザビシクロ［３．２．１］オクタン、１－プロピル－３－アザビシクロ［３．２．２］ノナンなどの多環アミン化合物；などが挙げられる。 Specific examples of the compound represented by the formula (a-2) include pyrrolidine, piperidine, hexamethyleneimine, heptamethyleneimine, dodecamethyleneimine, 3-methylpiperidine, 3,3,5-trimethylhexamethyleneimine. Compounds having one nitrogen atom such as hexadecamemethyleneimine, 2- (2-ethylhexyl) pyrrolidine, 3,5-bis (2-ethylhexyl) piperidine, 4-phenylpiperidine, morpholine, etc .; 4-propylpiperazine, N A compound having 2 nitrogen atoms, such as trimethylsilylpiperazine, N- (tert-butyldimethylsilyl) piperazine, etc .; a compound having 3 nitrogen atoms, such as 1,3-ditrimethylsilyl-1,3,5-triazinan; 1,3,3-trimethyl-6-aza Cyclo [3.2.1] octane, 1-propyl-3-azabicyclo [3.2.2] polycyclic amine compounds such as nonane; and the like.
　窒素含有化合物Ｘとしては、低燃費性能、ウェットグリップ特性等の諸特性をバランス良く発現する架橋ゴムが得られる点で、環状アミン化合物であることが好ましい。窒素含有化合物Ｘとして環状アミン化合物を用いた場合、生成する有機金属アミド化合物の重合活性が高く、結果として分子量分布が狭くなることにより、上記の如く諸特性が改善されたことが推測される。なお、窒素含有化合物Ｘとしては、１種を単独で使用してもよく、２種以上を組み合わせて使用してもよい。 The nitrogen-containing compound X is preferably a cyclic amine compound in terms of obtaining a crosslinked rubber that exhibits various properties such as low fuel consumption performance and wet grip properties. When a cyclic amine compound is used as the nitrogen-containing compound X, it is presumed that various properties have been improved as described above due to the high polymerization activity of the resulting organometallic amide compound, resulting in a narrow molecular weight distribution. In addition, as nitrogen-containing compound X, 1 type may be used independently and 2 or more types may be used in combination.
　金属化合物Ｙとしては、例えばメチルリチウム、エチルリチウム、ｎ－プロピルリチウム、ｎ－ブチルリチウム、ｓｅｃ－ブチルリチウム、ｔ－ブチルリチウムなどのアルキルリチウム、１，４－ジリチオブタン、フェニルリチウム、スチルベンリチウム、ナフチルリチウム、１，３－ビス（１－リチオ－１，３－ジメチルペンチル）ベンゼン、１，３－フェニレンビス（３－メチル－１－フェニルペンチリデン）ジリチウム、ナトリウムナフタレン、カリウムナフタレン、ジ－ｎ－ブチルマグネシウム、ジ－ｎ－ヘキシルマグネシウム、エトキシカリウム、ステアリン酸カルシウム等が挙げられる。これらの中でもリチウム化合物又はナトリウム化合物が好ましく、リチウム化合物が特に好ましい。 Examples of the metal compound Y include methyllithium, ethyllithium, n-propyllithium, n-butyllithium, sec-butyllithium, alkyllithium such as t-butyllithium, 1,4-dilithiobutane, phenyllithium, stilbenelithium, naphthyl. Lithium, 1,3-bis (1-lithio-1,3-dimethylpentyl) benzene, 1,3-phenylenebis (3-methyl-1-phenylpentylidene) dilithium, sodium naphthalene, potassium naphthalene, di-n- Examples include butyl magnesium, di-n-hexyl magnesium, ethoxy potassium, and calcium stearate. Among these, a lithium compound or a sodium compound is preferable, and a lithium compound is particularly preferable.
　予備重合では、１，３－ブタジエンを重合することによりブタジエンブロックを形成する。ブタジエンブロックを有する変性共役ジエン開始剤を用いて以下の工程Ｂで重合を行うことにより、二律背反である加工性とヒステリシスロス低減とがバランス良く改善された変性共役ジエン系重合体を得ることができる。
　なお、本明細書において「１，３－ブタジエンを重合する」とは、本開示の効果を損なわない範囲内である限り、変性共役ジエン開始剤が有するブタジエンブロックが１，３－ブタジエン単位とは異なる構成単位を有することを許容するものである。１，３－ブタジエン単位とは異なる構成単位としては、１，３－ブタジエンとは異なる共役ジエン化合物に由来する共役ジエン単位が挙げられ、例えば、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、１，３－ヘキサジエン、１，３－ヘプタジエン、２－フェニル－１，３－ブタジエン、３－メチル－１，３－ペンタジエン、又は２－クロロ－１，３－ブタジエンに由来する構成単位等が挙げられる。 In the prepolymerization, 1,3-butadiene is polymerized to form a butadiene block. By performing polymerization in the following step B using a modified conjugated diene initiator having a butadiene block, a modified conjugated diene-based polymer improved in a well-balanced processability and hysteresis loss reduction can be obtained. .
In the present specification, “polymerize 1,3-butadiene” means that the butadiene block of the modified conjugated diene initiator is a 1,3-butadiene unit as long as the effect of the present disclosure is not impaired. It is allowed to have different structural units. Examples of structural units different from 1,3-butadiene units include conjugated diene units derived from conjugated diene compounds different from 1,3-butadiene, such as isoprene, 2,3-dimethyl-1,3-butadiene. 1,3-pentadiene, 1,3-hexadiene, 1,3-heptadiene, 2-phenyl-1,3-butadiene, 3-methyl-1,3-pentadiene, or 2-chloro-1,3-butadiene Examples are derived structural units.
　具体的には、変性共役ジエン開始剤が有するブタジエンブロックにおける、１，３－ブタジエン単位とは異なる構成単位の含有割合は、ブタジエンブロックを構成する全構成単位のうち、１０質量％未満であることが好ましく、５質量％未満であることがより好ましく、１質量％未満であることがさらに好ましい。変性共役ジエン開始剤が有するブタジエンブロックは、低燃費性能、耐摩耗性及びウェットグリップ性の改善効果が高い点で、１，３－ブタジエン単位のみからなることが特に好ましい。 Specifically, the content ratio of the structural unit different from the 1,3-butadiene unit in the butadiene block of the modified conjugated diene initiator is less than 10% by mass of the total structural units constituting the butadiene block. Is preferably less than 5% by mass, and more preferably less than 1% by mass. The butadiene block contained in the modified conjugated diene initiator is particularly preferably composed of only 1,3-butadiene units from the viewpoint of high fuel economy performance, wear resistance, and wet grip properties.
　予備重合に際し、使用する重合法としては、溶液重合法、気相重合法、バルク重合法のいずれを用いてもよいが、溶液重合法が特に好ましい。使用する有機溶媒としては、反応に不活性な有機溶剤であればよく、例えば脂肪族炭化水素、脂環式炭化水素、芳香族炭化水素などを用いることができる。中でも、炭素数３～８の炭化水素が好ましく、その具体例としては、例えばプロパン、ｎ－ブタン、イソブタン、ｎ－ペンタン、イソペンタン、ｎ－へキサン、シクロへキサン、プロペン、１－ブテン、イソブテン、トランス－２－ブテン、シス－２－ブテン、１－ペンチン、２－ペンチン、１－ヘキセン、２－ヘキセン、ベンゼン、トルエン、キシレン、エチルベンゼン、ヘプタン、シクロペンタン、メチルシクロペンタン、メチルシクロヘキサン、１－ペンテン、２－ペンテン、シクロヘキセン等が挙げられる。なお、有機溶媒としては、１種を単独で又は２種以上を組み合わせて使用することができる。 As the polymerization method used in the preliminary polymerization, any of solution polymerization method, gas phase polymerization method and bulk polymerization method may be used, but solution polymerization method is particularly preferable. The organic solvent to be used may be any organic solvent inert to the reaction. For example, aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, and the like can be used. Among these, hydrocarbons having 3 to 8 carbon atoms are preferable, and specific examples thereof include, for example, propane, n-butane, isobutane, n-pentane, isopentane, n-hexane, cyclohexane, propene, 1-butene and isobutene. , Trans-2-butene, cis-2-butene, 1-pentyne, 2-pentyne, 1-hexene, 2-hexene, benzene, toluene, xylene, ethylbenzene, heptane, cyclopentane, methylcyclopentane, methylcyclohexane, 1 -Pentene, 2-pentene, cyclohexene and the like. In addition, as an organic solvent, 1 type can be used individually or in combination of 2 or more types.
　予備重合において、窒素含有化合物Ｘ、金属化合物Ｙ、及び１，３－ブタジエンの使用割合は、変性共役ジエン開始剤が有する共役ジエンブロックの長さ等に応じて設定することができる。具体的には、金属化合物Ｙの使用割合は、予備重合に使用する１，３－ブタジエン１００ｇに対して、１０～２０００ｍｍｏｌとすることが好ましく、５０～１０００ｍｍｏｌとすることがより好ましく、１００～９００ｍｍｏｌとすることがさらに好ましい。また、窒素含有化合物Ｘの使用割合は、金属化合物Ｙの１モルに対して、０．１～１０モルであることが好ましく、０．５～５モルであることがより好ましい。 In the prepolymerization, the usage ratio of the nitrogen-containing compound X, the metal compound Y, and 1,3-butadiene can be set according to the length of the conjugated diene block of the modified conjugated diene initiator. Specifically, the use ratio of the metal compound Y is preferably 10 to 2000 mmol, more preferably 50 to 1000 mmol, more preferably 100 to 900 mmol, with respect to 100 g of 1,3-butadiene used for the prepolymerization. More preferably. Further, the use ratio of the nitrogen-containing compound X is preferably 0.1 to 10 mol, more preferably 0.5 to 5 mol, with respect to 1 mol of the metal compound Y.
　予備重合における１，３－ブタジエンの使用割合は、次の工程Ｂにおいて変性共役ジエン開始剤を用いた共役ジエン化合物及び芳香族ビニル化合物の重合の際に使用する共役ジエン化合物と芳香族ビニル化合物との合計量に対して、０．１～５質量％とすることが好ましく、０．５～３質量％とすることがより好ましい。０．１質量％以上とすることにより、得られるゴム組成物の加工性の改善効果をより十分に得ることができ、５質量％以下とすることにより、加硫ゴムのヒステリシスロス低減をより十分に図ることができる。 The proportion of 1,3-butadiene used in the prepolymerization is determined in the following step B by using a conjugated diene compound and an aromatic vinyl compound used in the polymerization of a conjugated diene compound and an aromatic vinyl compound using a modified conjugated diene initiator. The total amount is preferably 0.1 to 5% by mass, and more preferably 0.5 to 3% by mass. By making the content 0.1% by mass or more, the effect of improving the workability of the resulting rubber composition can be obtained more sufficiently, and by making it 5% by mass or less, the hysteresis loss of the vulcanized rubber can be sufficiently reduced. Can be aimed at.
　なお、本明細書において「窒素含有化合物Ｘと金属化合物Ｙとを混合して得られる化合物の存在下で１，３－ブタジエンを重合する」とは、（１）窒素含有化合物Ｘと金属化合物Ｙとを予め混合しておき、その混合物と１，３－ブタジエンとを混合することにより１，３－ブタジエンを重合する方法、（２）窒素含有化合物Ｘと１，３－ブタジエンとを予め混合しておき、その混合物と金属化合物Ｙとを混合することにより１，３－ブタジエンを重合する方法、の両方を含む意味である。 In this specification, “polymerizing 1,3-butadiene in the presence of a compound obtained by mixing nitrogen-containing compound X and metal compound Y” means (1) nitrogen-containing compound X and metal compound Y. A method of polymerizing 1,3-butadiene by mixing the mixture with 1,3-butadiene, and (2) mixing nitrogen-containing compound X and 1,3-butadiene in advance. In addition, it means to include both a method of polymerizing 1,3-butadiene by mixing the mixture and the metal compound Y.
　予備重合は、共役ジエンブロック中のビニル結合の含有率を表すビニル結合含量を調整すること等を目的として、ランダマイザーの存在下で行ってもよい。ランダマイザーの例としては、例えばジメトキシベンゼン、テトラヒドロフラン、ジメトキシエタン、ジエチレングリコールジブチルエーテル、ジエチレングリコールジメチルエーテル、２，２－ジ（テトラヒドロフリル）プロパン、２－（２－エトキシエトキシ）－２－メチルプロパン、トリエチルアミン、ピリジン、Ｎ－メチルモルホリン、テトラメチルエチレンジアミン等が挙げられる。これらは、１種を単独で又は２種以上を組み合わせて使用できる。 The prepolymerization may be performed in the presence of a randomizer for the purpose of adjusting the vinyl bond content representing the vinyl bond content in the conjugated diene block. Examples of randomizers include, for example, dimethoxybenzene, tetrahydrofuran, dimethoxyethane, diethylene glycol dibutyl ether, diethylene glycol dimethyl ether, 2,2-di (tetrahydrofuryl) propane, 2- (2-ethoxyethoxy) -2-methylpropane, triethylamine, Examples include pyridine, N-methylmorpholine, and tetramethylethylenediamine. These can be used individually by 1 type or in combination of 2 or more types.
　予備重合を溶媒中で行う場合、反応溶液中のモノマー濃度は、生産性と重合コントロールの容易性のバランスを維持する観点から、５～５０質量％であることが好ましく、１０～３０質量％であることがより好ましい。重合反応の温度は、－２０℃～１５０℃であることが好ましく、０～１２０℃であることがより好ましい。また、重合反応は、単量体を実質的に液相に保つのに十分な圧力の下で行うことが好ましい。このような圧力は、重合反応に対して不活性なガスによって、反応器内を加圧する等の方法によって得ることができる。 When the prepolymerization is performed in a solvent, the monomer concentration in the reaction solution is preferably 5 to 50% by mass from the viewpoint of maintaining the balance between productivity and ease of polymerization control, and is preferably 10 to 30% by mass. More preferably. The temperature of the polymerization reaction is preferably −20 ° C. to 150 ° C., more preferably 0 to 120 ° C. The polymerization reaction is preferably performed under a pressure sufficient to keep the monomer in a substantially liquid phase. Such a pressure can be obtained by a method such as pressurizing the inside of the reactor with a gas inert to the polymerization reaction.
＜工程Ｂ＞
　本工程では、工程Ａで得られた変性共役ジエン開始剤の存在下で、共役ジエン化合物及び芳香族ビニル化合物を重合する。この重合反応により、共役ジエン単位と芳香族ビニル単位とを有する共重合体鎖の一方の末端に、窒素含有基を末端に有するブタジエンブロックが結合され、他方の末端が活性末端である共役ジエン系重合体を得ることができる。 <Process B>
In this step, the conjugated diene compound and the aromatic vinyl compound are polymerized in the presence of the modified conjugated diene initiator obtained in Step A. By this polymerization reaction, a conjugated diene system in which a butadiene block having a nitrogen-containing group at one end is bonded to one end of a copolymer chain having a conjugated diene unit and an aromatic vinyl unit, and the other end is an active end A polymer can be obtained.
　本工程の重合に使用する共役ジエン化合物としては、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、１，３－ヘキサジエン、１，３－ヘプタジエン、２－フェニル－１，３－ブタジエン、３－メチル－１，３－ペンタジエン、２－クロロ－１，３－ブタジエン等が挙げられる。中でも、１，３－ブタジエン、イソプレン及び２，３－ジメチル－１，３－ブタジエンの少なくともいずれかであることが好ましい。なお、共役ジエン化合物としては、１種を単独で使用してもよく、２種以上を組み合わせて使用してもよい。 Examples of the conjugated diene compound used in the polymerization in this step include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, 1,3- Examples include heptadiene, 2-phenyl-1,3-butadiene, 3-methyl-1,3-pentadiene, 2-chloro-1,3-butadiene and the like. Among these, at least one of 1,3-butadiene, isoprene and 2,3-dimethyl-1,3-butadiene is preferable. In addition, as a conjugated diene compound, 1 type may be used independently and 2 or more types may be used in combination.
　芳香族ビニル化合物としては、例えばスチレン、２－メチルスチレン、３－メチルスチレン、４－メチルスチレン、α－メチルスチレン、２，４－ジメチルスチレン、２，４－ジイソプロピルスチレン、４－ｔ－ブチルスチレン、５－ｔ－ブチル－２－メチルスチレン、ビニルエチルベンゼン、ジビニルベンゼン、トリビニルベンゼン、ジビニルナフタレン、ｔ－ブトキシスチレン、ビニルベンジルジメチルアミン、（４－ビニルベンジル）ジメチルアミノエチルエーテル、Ｎ，Ｎ－ジメチルアミノエチルスチレン、Ｎ，Ｎ－ジメチルアミノメチルスチレン、２－エチルスチレン、３－エチルスチレン、４－エチルスチレン、２－ｔ－ブチルスチレン、３－ｔ－ブチルスチレン、ビニルキシレン、ビニルナフタレン、ビニルピリジン、ジフェニルエチレン、３級アミノ基含有ジフェニルエチレン（例えば、１－（４－Ｎ，Ｎ－ジメチルアミノフェニル）－１－フェニルエチレンなど）等が挙げられる。芳香族ビニル化合物としては、これらの中でもスチレン及びα－メチルスチレンの少なくともいずれかであることが好ましい。芳香族ビニル化合物は、１種を単独で使用してもよく、２種以上を組み合わせて使用してもよい。 Examples of the aromatic vinyl compound include styrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, α-methylstyrene, 2,4-dimethylstyrene, 2,4-diisopropylstyrene, and 4-t-butylstyrene. 5-t-butyl-2-methylstyrene, vinylethylbenzene, divinylbenzene, trivinylbenzene, divinylnaphthalene, t-butoxystyrene, vinylbenzyldimethylamine, (4-vinylbenzyl) dimethylaminoethyl ether, N, N- Dimethylaminoethylstyrene, N, N-dimethylaminomethylstyrene, 2-ethylstyrene, 3-ethylstyrene, 4-ethylstyrene, 2-t-butylstyrene, 3-t-butylstyrene, vinylxylene, vinylnaphthalene, vinyl Pyridine, diph Niruechiren, tertiary amino group-containing diphenylethylene (e.g., 1- (4-N, N- dimethylaminophenyl) -1-phenylethylene, etc.) and the like. Among these, the aromatic vinyl compound is preferably at least one of styrene and α-methylstyrene. An aromatic vinyl compound may be used individually by 1 type, and may be used in combination of 2 or more type.
　本工程の重合は、アニオン重合におけるリビング性が高い点で、中でも１，３－ブタジエンとスチレンとを用いた共重合であることが好ましい。共役ジエン化合物及び芳香族ビニル化合物の重合はランダム重合であることが好ましい。 The polymerization in this step is preferably a copolymerization using 1,3-butadiene and styrene, in view of high living property in anionic polymerization. The polymerization of the conjugated diene compound and the aromatic vinyl compound is preferably random polymerization.
　重合に際し、芳香族ビニル化合物の使用割合は、得られる加硫ゴムの低ヒステリシスロス特性とウェットグリップ性とのバランスを良好にする観点から、重合に使用する共役ジエン化合物及び芳香族ビニル化合物の合計量に対して、３～５５質量％とすることが好ましく、５～５０質量％とすることがより好ましい。なお、重合体中における、芳香族ビニル化合物に由来する構造単位の含有割合は１Ｈ－ＮＭＲによって測定した値である。 In the polymerization, the proportion of the aromatic vinyl compound used is the sum of the conjugated diene compound and the aromatic vinyl compound used for the polymerization from the viewpoint of improving the balance between the low hysteresis loss property of the vulcanized rubber and the wet grip property. The amount is preferably 3 to 55% by mass, more preferably 5 to 50% by mass. The content ratio of the structural unit derived from the aromatic vinyl compound in the polymer is a value measured by 1 H-NMR.
　上記重合に際しては、モノマーとして、共役ジエン化合物及び芳香族ビニル化合物以外の化合物（以下、「他のモノマー」ともいう。）を使用してもよい。他のモノマーとしては、例えばアクリロニトリル、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、１．５－ヘキサジエン、１，６－へプタジエン等が挙げられる。他のモノマーの使用割合は、工程Ｂの重合に使用するモノマーの全体量に対して、１０質量％以下とすることが好ましく、５質量％以下とすることがより好ましい。 In the polymerization, a compound other than the conjugated diene compound and the aromatic vinyl compound (hereinafter, also referred to as “other monomer”) may be used as the monomer. Examples of other monomers include acrylonitrile, methyl (meth) acrylate, ethyl (meth) acrylate, 1.5-hexadiene, 1,6-heptadiene, and the like. The proportion of other monomers used is preferably 10% by mass or less, and more preferably 5% by mass or less, based on the total amount of monomers used in the polymerization in Step B.
　使用する重合法としては、溶液重合法、気相重合法、バルク重合法のいずれを用いてもよいが、溶液重合法が特に好ましい。また、重合形式としては、回分式及び連続式のいずれを用いてもよい。溶液重合法を用いる場合、具体的な重合方法の一例としては、有機溶媒中において、共役ジエン化合物及び芳香族ビニル化合物を含むモノマーを、重合開始剤及び必要に応じて用いられるランダマイザーの存在下で重合する方法が挙げられる。 As the polymerization method to be used, any of solution polymerization method, gas phase polymerization method and bulk polymerization method may be used, but the solution polymerization method is particularly preferable. Moreover, as a polymerization form, you may use any of a batch type and a continuous type. When using the solution polymerization method, an example of a specific polymerization method is as follows: a monomer containing a conjugated diene compound and an aromatic vinyl compound in an organic solvent in the presence of a polymerization initiator and a randomizer used as necessary. The method of superposing | polymerizing is mentioned.
　工程Ｂでは、重合開始剤として、工程Ａで得られた変性共役ジエン開始剤を用いる。重合開始剤の合計の使用割合は、目的とする分子量に応じて適宜設定することができる。なお、変性共役ジエン開始剤は、１種のみを使用してもよく、２種以上を組み合わせて使用してもよい。 In Step B, the modified conjugated diene initiator obtained in Step A is used as a polymerization initiator. The total use ratio of the polymerization initiator can be appropriately set according to the target molecular weight. In addition, a modified conjugated diene initiator may use only 1 type and may use it in combination of 2 or more type.
　ランダマイザーは、共役ジエン単位と芳香族ビニル単位との共重合体鎖におけるビニル結合含量の調整等を目的として用いることができる。ランダマイザーの具体例については、工程Ａの説明が適用される。また、重合に使用する有機溶媒は、反応に不活性な有機溶剤であればよく、その具体例としては、工程Ａで例示した化合物等が挙げられる。溶液重合とする場合の反応溶媒中のモノマー濃度、重合反応の温度等の条件については、工程Ａの予備重合の説明が適用される。 The randomizer can be used for the purpose of adjusting the vinyl bond content in the copolymer chain of conjugated diene units and aromatic vinyl units. The description of the process A is applied to a specific example of the randomizer. Moreover, the organic solvent used for superposition | polymerization should just be an organic solvent inactive to reaction, The compound etc. which were illustrated at the process A as the specific example are mentioned. For the conditions such as the monomer concentration in the reaction solvent and the temperature of the polymerization reaction in the case of solution polymerization, the description of the preliminary polymerization in Step A is applied.
　共役ジエン化合物及び芳香族ビニル化合物の重合後において、重合反応を停止させる前に共役ジエン化合物を追添し、更に重合を行ってもよい。この共役ジエン化合物の追添及び重合により、共役ジエン化合物及び芳香族ビニル化合物の共重合体鎖の重合開始末端にブタジエンブロックを有し、かつ重合終了末端に、共役ジエン化合物を重合して形成された共役ジエンブロックを有する変性共役ジエン系重合体を得ることができる。追添する共役ジエン化合物としては、工程Ｂの上記重合で使用してもよい共役ジエン化合物として例示した化合物等が挙げられ、これらのうち、低燃費性能、耐摩耗性及びウェットグリップ性の改善効果が高い点で１，３－ブタジエンが好ましい。
　追添での共役ジエン化合物の使用割合は、変性共役ジエン開始剤の調製に使用する１，３－ブタジエン１ｇに対して、０．１～１５ｇとすることが好ましく、１～１０ｇとすることがより好ましい。 After the polymerization of the conjugated diene compound and the aromatic vinyl compound, the conjugated diene compound may be added before the polymerization reaction is stopped, and further polymerization may be performed. By adding and polymerizing the conjugated diene compound, the copolymer chain of the conjugated diene compound and the aromatic vinyl compound has a butadiene block at the polymerization start terminal, and is formed by polymerizing the conjugated diene compound at the polymerization end terminal. A modified conjugated diene polymer having a conjugated diene block can be obtained. Examples of the conjugated diene compound to be added include compounds exemplified as the conjugated diene compound that may be used in the polymerization in the step B, and among these, low fuel consumption performance, wear resistance, and wet grip properties are improved. 1,3-butadiene is preferred because of its high C ratio.
The proportion of the conjugated diene compound used in the addition is preferably 0.1 to 15 g and preferably 1 to 10 g with respect to 1 g of 1,3-butadiene used for preparing the modified conjugated diene initiator. More preferred.
　なお、本開示の効果を損なわない範囲である限り、工程Ｂの重合で重合終了末端に形成されてもよい共役ジエンブロックが共役ジエン単位とは異なる構成単位を有することは許容される。具体的には、工程Ｂの重合で重合終了末端に共役ジエンブロックを形成する場合、当該共役ジエンブロックにおける、共役ジエン単位とは異なる構成単位の含有割合は、共役ジエンブロックを構成する全構成単位のうち、５質量％未満であることが好ましく、２質量％未満であることがより好ましく、１質量％未満であることが更に好ましい。
　工程Ｂの重合で重合終了末端に形成されてもよい共役ジエンブロックが、１，３－ブタジエンを重合したブタジエンブロックである場合、当該ブタジエンブロックにおける１，３－ブタジエン単位の含有割合は、８０質量％以上であることが好ましく、９０質量％以上であることがより好ましく、９５質量％以上であることが更に好ましく、１，３－ブタジエン単位のみからなることが特に好ましい。 As long as the effect of the present disclosure is not impaired, the conjugated diene block that may be formed at the polymerization end terminal in the polymerization in Step B is allowed to have a structural unit different from the conjugated diene unit. Specifically, when a conjugated diene block is formed at the polymerization end terminal in the polymerization in Step B, the content ratio of the structural unit different from the conjugated diene unit in the conjugated diene block is all the structural units constituting the conjugated diene block. Of these, the content is preferably less than 5% by mass, more preferably less than 2% by mass, and still more preferably less than 1% by mass.
When the conjugated diene block that may be formed at the polymerization end terminal in the polymerization in the step B is a butadiene block obtained by polymerizing 1,3-butadiene, the content of 1,3-butadiene units in the butadiene block is 80 masses. %, More preferably 90% by mass or more, still more preferably 95% by mass or more, and particularly preferably only 1,3-butadiene units.
　工程Ｂの重合反応により、一方の末端に窒素含有基を有し、他方の末端が活性末端である変性共役ジエン系重合体を得ることができる。活性末端を有する変性共役ジエン系重合体のゲルパーミエーションクロマトグラフィー（ＧＰＣ）によるポリスチレン換算の重量平均分子量（Ｍｗ）は、好ましくは５．０×１０４～１．０×１０６である。Ｍｗが５．０×１０４よりも小さいと、加硫ゴムの引張強度、低発熱性及び耐摩耗性が低下しやすい傾向にあり、１．０×１０６よりも大きいと、得られるゴム組成物の加工性が低下しやすい傾向にある。より好ましくは、８．０×１０４～８．０×１０５であり、さらに好ましくは、１．０×１０５～５．０×１０５である。 By the polymerization reaction in step B, a modified conjugated diene polymer having a nitrogen-containing group at one end and the active end at the other end can be obtained. The weight-average molecular weight (Mw) in terms of polystyrene determined by gel permeation chromatography (GPC) of the modified conjugated diene polymer having an active end is preferably 5.0 × 10 4 to 1.0 × 10 6 . When Mw is smaller than 5.0 × 10 4, the tensile strength, low heat build-up and wear resistance of the vulcanized rubber tend to be lowered, and when larger than 1.0 × 10 6 , the resulting rubber composition There exists a tendency for the workability of a thing to fall easily. More preferably, it is 8.0 × 10 4 to 8.0 × 10 5 , and still more preferably 1.0 × 10 5 to 5.0 × 10 5 .
　本工程により得られる変性共役ジエン系重合体につき、ブタジエン単位におけるビニル結合含量は、３０～７０質量％であることが好ましく、３３～６８質量％であることがより好ましく、３５～６５質量％であることがさらに好ましい。ビニル結合含量が３０質量％未満であると、グリップ特性が低くなる傾向があり、７０質量％を超えると、得られる加硫ゴムの耐摩耗性が低下する傾向にある。 With respect to the modified conjugated diene polymer obtained by this step, the vinyl bond content in the butadiene unit is preferably 30 to 70% by mass, more preferably 33 to 68% by mass, and 35 to 65% by mass. More preferably it is. When the vinyl bond content is less than 30% by mass, the grip characteristics tend to be low, and when it exceeds 70% by mass, the wear resistance of the resulting vulcanized rubber tends to decrease.
＜その他の工程＞
・末端変性工程
　工程Ｂで得られた活性末端を有する変性共役ジエン系重合体につき、アルコール等を用いて重合を停止させてもよいが、変性共役ジエン系重合体が有する活性末端と、シリカと相互作用する官能基を有し、かつ重合体の活性末端と反応し得る化合物（以下、「末端変性化合物」ともいう。）と、を反応させてもよい。こうした工程を経ることにより、本開示の変性共役ジエン系重合体として、シリカと相互作用する官能基で両末端が変性された変性重合体を得ることができる。 <Other processes>
Terminal modification step The modified conjugated diene polymer having an active terminal obtained in Step B may be terminated by using alcohol or the like, but the active terminal of the modified conjugated diene polymer, silica, A compound having an interacting functional group and capable of reacting with the active terminal of the polymer (hereinafter also referred to as “terminal-modified compound”) may be reacted. Through these steps, a modified polymer in which both ends are modified with a functional group that interacts with silica can be obtained as the modified conjugated diene polymer of the present disclosure.
　なお、本明細書において「シリカと相互作用する官能基」とは、窒素、硫黄、リン、酸素などのシリカと相互作用する元素を有する基を意味する。「相互作用」とは、分子間で共有結合を形成するか、又は共有結合よりも弱い分子間力（例えば、イオン－双極子相互作用、双極子－双極子相互作用、水素結合、ファンデルワールス力等といった分子間に働く電磁気学的な力）を形成することを意味する。 In the present specification, the “functional group that interacts with silica” means a group having an element that interacts with silica such as nitrogen, sulfur, phosphorus, and oxygen. “Interaction” refers to an intermolecular force that forms a covalent bond between molecules or is weaker than a covalent bond (eg, ion-dipole interaction, dipole-dipole interaction, hydrogen bond, van der Waals This means that an electromagnetic force between molecules such as force is formed.
　末端変性化合物は、窒素原子、硫黄原子、リン原子、酸素原子及びケイ素原子からなる群より選ばれる一種を有する化合物であることが好ましい。これらの具体例としては、例えば、下記（Ｉ）～（ＩＶ）のそれぞれの化合物等が挙げられる。 The terminal-modified compound is preferably a compound having one kind selected from the group consisting of a nitrogen atom, a sulfur atom, a phosphorus atom, an oxygen atom and a silicon atom. Specific examples thereof include, for example, the following compounds (I) to (IV).
（Ｉ）　下記式（１）で表される化合物（Ｂ－１）；
Figure JPOXMLDOC01-appb-C000003
 （式（１）中、Ａ１は、窒素原子、リン原子及び硫黄原子からなる群より選択される少なくとも一種の原子を有し、活性水素を有さず、かつＲ３に対して窒素原子、リン原子又は硫黄原子で結合する１価の官能基である。Ｒ１及びＲ２はヒドロカルビル基であり、Ｒ３はヒドロカルビレン基であり、ｎは０～２の整数である。但し、Ｒ１及びＲ２が複数存在する場合、複数のＲ１及びＲ２は、それぞれ同じでも異なっていてもよい。） (I) Compound (B-1) represented by the following formula (1);
Figure JPOXMLDOC01-appb-C000003
 (In Formula (1), A 1 has at least one atom selected from the group consisting of a nitrogen atom, a phosphorus atom, and a sulfur atom, does not have active hydrogen, and is a nitrogen atom with respect to R 3 ; A monovalent functional group bonded by a phosphorus atom or a sulfur atom, R 1 and R 2 are hydrocarbyl groups, R 3 is a hydrocarbylene group, and n is an integer of 0 to 2, provided that R 1 When a plurality of 1 and R 2 are present, the plurality of R 1 and R 2 may be the same or different.)
（ＩＩ）　分子中に、環状エーテル基、（チオ）カルボニル基及びイソ（チオ）シアナート基からなる群より選択される少なくとも１種である官能基Ｐと、窒素原子、リン原子、酸素原子及び硫黄原子からなる群より選択される少なくとも一種の原子（但し、窒素原子、リン原子及び硫黄原子は、少なくともいずれかが３置換のヒドロカルビルシリル基で保護されていてもよい。）を有し、かつ活性水素を有していない、上記官能基Ｐとは異なる基Ｑと、を各々１つ以上有する化合物（Ｂ－２）；
（ＩＩＩ）　分子中に、イソ（チオ）シアナート基を２つ以上有する化合物（Ｂ－３）；
（ＩＶ）　ケイ素－窒素結合を有する化合物（Ｂ－４）； (II) In the molecule, a functional group P which is at least one selected from the group consisting of a cyclic ether group, a (thio) carbonyl group and an iso (thio) cyanate group, a nitrogen atom, a phosphorus atom, an oxygen atom and sulfur And having at least one atom selected from the group consisting of atoms (provided that at least one of a nitrogen atom, a phosphorus atom and a sulfur atom may be protected by a trisubstituted hydrocarbylsilyl group) and an activity A compound (B-2) having no hydrogen and having at least one group Q different from the functional group P;
(III) Compound (B-3) having two or more iso (thio) cyanate groups in the molecule;
(IV) Compound (B-4) having a silicon-nitrogen bond;
　なお、末端変性化合物としては、これらの１種を単独で又は２種以上を組み合わせて使用することができる。本明細書において、（チオ）カルボニル基は、カルボニル基及びチオカルボニル基を示し、イソ（チオ）シアナート基は、イソシアナート基及びイソチオシアナート基を示す。 In addition, as a terminal modified compound, these 1 type can be used individually or in combination of 2 or more types. In the present specification, the (thio) carbonyl group represents a carbonyl group and a thiocarbonyl group, and the iso (thio) cyanate group represents an isocyanate group and an isothiocyanate group.
　上記式（１）において、Ｒ１及びＲ２のヒドロカルビル基は、炭素数１～２０の直鎖状若しくは分岐状のアルキル基、炭素数３～２０のシクロアルキル基又は炭素数６～２０のアリール基であることが好ましい。
　Ｒ３は、炭素数１～２０の直鎖状若しくは分岐状のアルカンジイル基、炭素数３～２０のシクロアルキレン基又は炭素数６～２０のアリーレン基であることが好ましい。
　ｎは、共役ジエン系重合体との反応性を高める観点から、０又は１が好ましい。
　Ａ１は、窒素原子、リン原子及び硫黄原子からなる群より選択される少なくとも一種の原子（以下、特定原子Ｃともいう。）を有し、特定原子ＣでＲ３に結合する。特定原子Ｃは活性水素に結合しておらず、また保護基で保護されていてもよい。 In the above formula (1), the hydrocarbyl group of R 1 and R 2 is a linear or branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, or an aryl having 6 to 20 carbon atoms. It is preferably a group.
R 3 is preferably a linear or branched alkanediyl group having 1 to 20 carbon atoms, a cycloalkylene group having 3 to 20 carbon atoms, or an arylene group having 6 to 20 carbon atoms.
n is preferably 0 or 1 from the viewpoint of increasing the reactivity with the conjugated diene polymer.
A 1 has at least one atom selected from the group consisting of a nitrogen atom, a phosphorus atom and a sulfur atom (hereinafter also referred to as a specific atom C), and is bonded to R 3 with the specific atom C. The specific atom C is not bonded to active hydrogen and may be protected with a protecting group.
　なお、本明細書において「保護基」とは、Ａ１を重合活性末端に対して不活性な官能基に変換しておく官能基であり、例えば３置換のヒドロカルビルシリル基等が挙げられる。
　Ａ１は、中でも、オニウム塩生成剤によってオニウムイオンになり得る基であることが好ましい。末端変性化合物がこのような基（Ａ１）を有することにより、得られる共役ジエン系重合体の形状保持性を改善することができる。 In the present specification, the “protecting group” is a functional group that converts A 1 into a functional group that is inactive with respect to the polymerization active terminal, and examples thereof include a trisubstituted hydrocarbylsilyl group.
In particular, A 1 is preferably a group capable of becoming an onium ion by the onium salt generator. When the terminal modified compound has such a group (A 1 ), the shape retention of the resulting conjugated diene polymer can be improved.
　化合物（Ｂ－１）の具体例としては、１級アミノ基の２つの水素原子が２つの保護基によって置換されてなる窒素含有基、２級アミノ基の１つの水素原子が１つの保護基によって置換されてなる窒素含有基又は３級アミノ基と、アルコキシシリル基とを有する化合物として、例えば、Ｎ，Ｎ－ビス（トリメチルシリル）アミノプロピルトリメトキシシラン、Ｎ，Ｎ－ビス（トリメチルシリル）アミノプロピルメチルジエトキシシラン、Ｎ，Ｎ’，Ｎ’－トリス（トリメチルシリル）－Ｎ－（２－アミノエチル）－３－アミノプロピルトリエトキシシラン、３－（４－トリメチルシリル－１－ピペラジノ）プロピルメチルジメトキシシラン、及びこれらの化合物中のアルキル基、アルカンジイル基を、各々炭素数１～６のアルキル基、炭素数１～６のアルカンジイル基に置き換えた化合物等が挙げられる。 Specific examples of the compound (B-1) include a nitrogen-containing group in which two hydrogen atoms of a primary amino group are substituted by two protecting groups, and one hydrogen atom of a secondary amino group is substituted by one protecting group. Examples of the compound having a substituted nitrogen-containing group or tertiary amino group and an alkoxysilyl group include N, N-bis (trimethylsilyl) aminopropyltrimethoxysilane and N, N-bis (trimethylsilyl) aminopropylmethyl. Diethoxysilane, N, N ′, N′-tris (trimethylsilyl) -N- (2-aminoethyl) -3-aminopropyltriethoxysilane, 3- (4-trimethylsilyl-1-piperazino) propylmethyldimethoxysilane, And the alkyl group and alkanediyl group in these compounds are each an alkyl group having 1 to 6 carbon atoms, Compounds obtained by replacing the alkanediyl group ~ 6.
　炭素－窒素二重結合を有する基又は窒素含有複素環基と、アルコキシシリル基とを有する化合物としては、例えば、Ｎ－（１，３－ジメチルブチリデン）－３－（トリエトキシシリル）－１－プロパンアミン、Ｎ－（１－メチルプロピリデン）－３－（トリエトキシシリル）－１－プロパンアミン、Ｎ－（４－Ｎ，Ｎ－ジメチルアミノベンジリデン）－３－（トリエトキシシリル）－１－プロパンアミン、Ｎ－（シクロヘキシリデン）－３－（トリエトキシシリル）－１－プロパンアミン、Ｎ－（３－トリメトキシシリルプロピル）－４，５－ジヒドロイミダゾール、Ｎ－（３－トリメトキシシリルプロピル）イミダゾール、３－ヘキサメチレンイミノプロピルトリメトキシシラン、３－ヘキサメチレンイミノプロピルメチルジメトキシシラン、３－（１－ピペリジノ）プロピルトリメトキシシラン、３－（１－ヘキサメチレンイミノ）プロピルトリメトキシシラン、３－（１－ピペラジニル）プロピルトリメトキシシラン、３－モルホリノプロピルトリメトキシシラン、及びこれらの化合物中のアルキル基、アルカンジイル基を、各々炭素数１～６のアルキル基、炭素数１～６のアルカンジイル基に置き換えた化合物等が挙げられる。 Examples of the compound having a group having a carbon-nitrogen double bond or a nitrogen-containing heterocyclic group and an alkoxysilyl group include N- (1,3-dimethylbutylidene) -3- (triethoxysilyl) -1 -Propanamine, N- (1-methylpropylidene) -3- (triethoxysilyl) -1-propanamine, N- (4-N, N-dimethylaminobenzylidene) -3- (triethoxysilyl) -1 -Propanamine, N- (cyclohexylidene) -3- (triethoxysilyl) -1-propanamine, N- (3-trimethoxysilylpropyl) -4,5-dihydroimidazole, N- (3-trimethoxy Silylpropyl) imidazole, 3-hexamethyleneiminopropyltrimethoxysilane, 3-hexamethyleneiminopropylmethyldimethoxysilane 3- (1-piperidino) propyltrimethoxysilane, 3- (1-hexamethyleneimino) propyltrimethoxysilane, 3- (1-piperazinyl) propyltrimethoxysilane, 3-morpholinopropyltrimethoxysilane, and these And compounds in which the alkyl group and alkanediyl group in the compound are replaced with alkyl groups having 1 to 6 carbon atoms and alkanediyl groups having 1 to 6 carbon atoms, respectively.
　１級ホスフィノ基の２つの水素原子が２つの保護基によって置換されてなるリン含有基、２級ホスフィノ基の１つの水素原子が１つの保護基によって置換されてなるリン含有基、３級ホスフィノ基、又はチオール基の１つの水素原子が１つの保護基によって置換されてなる硫黄含有基と、アルコキシシリル基とを有する化合物としては、例えば、Ｐ，Ｐ－ビス（トリメチルシリル）ホスフィノプロピルメチルジメトキシシラン、Ｐ，Ｐ－ビス（トリメチルシリル）ホスフィノプロピルトリメトキシシラン、３－ジメチルフォスフィノプロピルトリメトキシシラン、３－ジメチルフォスフィノプロピルメチルジメトキシシラン、３－ジフェニルフォスフィノプロピルトリメトキシシラン、３－ジフェニルフォスフィノプロピルメチルジメトキシシラン、Ｓ－トリメチルシリルメルカプトプロピルメチルジメトキシシラン、Ｓ－トリメチルシリルメルカプトプロピルトリメトキシシラン、及びこれらの化合物中のアルキル基、アルカンジイル基を、各々炭素数１～６のアルキル基、炭素数１～６のアルカンジイル基に置き換えた化合物等を挙げることができる。イソ（チオ）シアナート基を有する化合物としては、例えば３－イソシアナトプロピルトリメトキシシラン、３－イソシアナトプロピルトリエトキシシラン等を挙げることができる。 A phosphorus-containing group in which two hydrogen atoms of a primary phosphino group are substituted by two protecting groups, a phosphorus-containing group in which one hydrogen atom of a secondary phosphino group is substituted by one protecting group, a tertiary phosphino group As a compound having a sulfur-containing group in which one hydrogen atom of a thiol group is substituted with one protecting group and an alkoxysilyl group, for example, P, P-bis (trimethylsilyl) phosphinopropylmethyldimethoxysilane , P, P-bis (trimethylsilyl) phosphinopropyltrimethoxysilane, 3-dimethylphosphinopropyltrimethoxysilane, 3-dimethylphosphinopropylmethyldimethoxysilane, 3-diphenylphosphinopropyltrimethoxysilane, 3-diphenylphos Finopropylmethyl dimethoxy Silane, S-trimethylsilyl mercaptopropylmethyldimethoxysilane, S-trimethylsilylmercaptopropyltrimethoxysilane, and alkyl groups and alkanediyl groups in these compounds are each an alkyl group having 1 to 6 carbon atoms and an alkyl group having 1 to 6 carbon atoms. Examples include compounds substituted with alkanediyl groups. Examples of the compound having an iso (thio) cyanate group include 3-isocyanatopropyltrimethoxysilane and 3-isocyanatopropyltriethoxysilane.
　化合物（Ｂ－２）は、上記基Ｑが、活性水素に結合していない窒素原子を含む基であることが好ましい。この場合の化合物（Ｂ－２）の具体例としては、環状エーテル基を有する化合物として、例えばテトラグリシジル－１，３－ビスアミノメチルシクロヘキサン等のエポキシアミン化合物などを；
（チオ）カルボニル基を有する化合物として、例えば４－Ｎ，Ｎ－ジメチルアミノベンゾフェノン等の４－アミノアセトフェノン；１，７－ビス（メチルエチルアミノ）－４－ヘプタノン等のビス（ジヒドロカルビルアミノアルキル）ケトン：２－ジメチルアミノエチルアクリレート等のジヒドロカルビルアミノアルキル（メタ）アクリレート；
１，３－ジメチル－２－イミダゾリジノン等のヒドロカルビルイミダゾリジノン；１－フェニル－２－ピロリドン等のＮ－ヒドロカルビルピロリドン；Ｎ－メチル－ε－カプロラクタム等のＮ－ヒロドカルビルカプトラクタム；Ｎ，Ｎ－ジエチルホルムアミド等のＮ－ジヒドロカルビルホルムアミド；Ｎ，Ｎ－ジメチルアセトアミド等のＮ，Ｎ－ジヒドロカルビルアセトアミド；Ｎ，Ｎ－ジメチルアクリルアミド等の（メタ）アクリルアミド；などを；イソ（チオ）シアナート基を有する化合物として、例えば３－イソシアナトプロピルトリメトキシシラン等を；挙げることができる。 In the compound (B-2), the group Q is preferably a group containing a nitrogen atom not bonded to active hydrogen. Specific examples of the compound (B-2) in this case include, as a compound having a cyclic ether group, for example, an epoxyamine compound such as tetraglycidyl-1,3-bisaminomethylcyclohexane and the like;
Examples of compounds having a (thio) carbonyl group include 4-aminoacetophenone such as 4-N, N-dimethylaminobenzophenone; bis (dihydrocarbylaminoalkyl) such as 1,7-bis (methylethylamino) -4-heptanone Ketone: dihydrocarbylaminoalkyl (meth) acrylate such as 2-dimethylaminoethyl acrylate;
Hydrocarbyl imidazolidinone such as 1,3-dimethyl-2-imidazolidinone; N-hydrocarbyl pyrrolidone such as 1-phenyl-2-pyrrolidone; N-hydrocarbyl captolactam such as N-methyl-ε-caprolactam; N N-dihydrocarbylformamide such as N, N-diethylformamide; N, N-dihydrocarbylacetamide such as N, N-dimethylacetamide; (meth) acrylamide such as N, N-dimethylacrylamide; etc .; iso (thio) cyanate Examples of the compound having a group include 3-isocyanatopropyltrimethoxysilane and the like.
　化合物（Ｂ－３）としては、例えば２，４－トリレンジイソシアナート、２，６－トリレンジイソシアナート、ジフェニルメタンジイソシアナート、ナフタレンジイソシアナート、トリフェニルメタントリイソシアナート、ｐ－フェニレンジイソシアナート、トリス（イソシアナートフェニル）チオホスフェート、キシレンジイソシアナート、ベンゼン－１，２，４－トリイソシアナート、ナフタレン－１，２，５，７－テトライソシアナート、１，４－フェニレンジイソチオシアナートなどを挙げることができる。 Examples of the compound (B-3) include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate, triphenylmethane triisocyanate, p-phenylene diisocyanate. Narate, tris (isocyanatophenyl) thiophosphate, xylene diisocyanate, benzene-1,2,4-triisocyanate, naphthalene-1,2,5,7-tetraisocyanate, 1,4-phenylenediisothiocyanate Narts can be mentioned.
　化合物（Ｂ－４）の具体例としては、例えば２－（２，２－ジメトキシ－１，２－アザシロリジン－１－イル）－Ｎ，Ｎ－ジエチルエタン－１－アミン、２－（２，２－ジメトキシ－１，２－アザシロリジン－１－イル）－Ｎ，Ｎ－ジメチルエタン－１－アミン、３－（２，２－ジメトキシ－１，２－アザシロリジン－１－イル）－Ｎ，Ｎ－ジエチルプロパン－１－アミン、２－（２，２－ジメトキシ－１－アザ－２－シラシクロヘキサン－１－イル）－Ｎ，Ｎ－ジエチルエタン－１－アミン、２，２－ジメトキシ－１－フェニル－１，２－アザシロリジン、Ｎ－ｎ－ブチル－アザ－２，２－ジアルコキシシラシクロペンタン、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、２，２－ジエトキシ－１－（３－トリエトキシシリルプロピル）－１－アザ－２－シラシクロペンタン、ヘキサメチルジシラザン、ノナメチルトリシラザン等が挙げられる。なお、末端変性化合物は、これらの１種を単独で又は２種以上を組み合わせて使用することができる。 Specific examples of the compound (B-4) include 2- (2,2-dimethoxy-1,2-azasilolidin-1-yl) -N, N-diethylethane-1-amine, 2- (2,2 -Dimethoxy-1,2-azasilolidin-1-yl) -N, N-dimethylethane-1-amine, 3- (2,2-dimethoxy-1,2-azasilolidin-1-yl) -N, N-diethyl Propan-1-amine, 2- (2,2-dimethoxy-1-aza-2-silacyclohexane-1-yl) -N, N-diethylethane-1-amine, 2,2-dimethoxy-1-phenyl- 1,2-azasilolidine, Nn-butyl-aza-2,2-dialkoxysilacyclopentane, 2,2-dimethoxy-1- (3-trimethoxysilylpropyl) -1-aza-2-silacyclopentane , 2, 2 Diethoxy-1- (3-triethoxysilylpropyl) -1-aza-2-silacyclopentane, hexamethyldisilazane, nona methyltrimethoxysilane silazane, and the like. In addition, a terminal modified compound can be used individually by 1 type or in combination of 2 or more types.
　末端変性化合物としては、シリカとの親和性が強い点において、特に化合物（Ｂ－１）及び化合物（Ｂ－４）よりなる群から選ばれる少なくとも一種を用いることが好ましく、化合物（Ｂ－１）を用いることがより好ましい。なお、化合物（Ｂ－１）を用いる場合に、変性共役ジエン系重合体のムーニー粘度を調整する目的で、化合物（Ｂ－１）と共に、四塩化ケイ素、多官能エポキシ化合物（例えば、テトラグリシジル－１，３－ビスアミノメチルシクロヘキサンなど）等のカップリング剤を併用してもよい。 As the terminally modified compound, it is particularly preferable to use at least one selected from the group consisting of the compound (B-1) and the compound (B-4) in view of strong affinity with silica, and the compound (B-1) It is more preferable to use When the compound (B-1) is used, for the purpose of adjusting the Mooney viscosity of the modified conjugated diene polymer, together with the compound (B-1), silicon tetrachloride, a polyfunctional epoxy compound (for example, tetraglycidyl- A coupling agent such as 1,3-bisaminomethylcyclohexane may be used in combination.
　末端変性化合物による変性反応は、例えば溶液反応として行うことができる。この溶液反応は、重合反応の終了後の未反応モノマーを含む溶液を用いて行ってもよく、当該溶液に含まれる共役ジエン系重合体を単離し、シクロヘキサン等の適当な溶媒に溶解した上で行ってもよい。また、変性反応は、回分式及び連続式のいずれを用いて行ってもよい。このとき、末端変性化合物の添加方法は特に制限されず、一括して添加する方法、分割して添加する方法、連続的に添加する方法などが挙げられる。 The modification reaction with the terminal modification compound can be performed, for example, as a solution reaction. This solution reaction may be carried out using a solution containing unreacted monomers after the completion of the polymerization reaction. The conjugated diene polymer contained in the solution is isolated and dissolved in a suitable solvent such as cyclohexane. You may go. Further, the denaturation reaction may be performed using either a batch system or a continuous system. At this time, the method for adding the terminal-modified compound is not particularly limited, and examples thereof include a method of adding all at once, a method of adding in divided portions, and a method of adding continuously.
　上記反応に際し、使用する末端変性化合物の量は、反応に使用する化合物の種類に応じて適宜設定すればよいが、重合開始剤が有する重合反応に関与する金属原子に対し、好ましくは０．１モル当量以上、より好ましくは０．３モル当量以上である。０．１モル当量以上とすることにより、変性反応を十分に進行させることができ、シリカの分散性を好適に改良することができる。 In the above reaction, the amount of the terminal-modified compound to be used may be appropriately set according to the kind of the compound to be used for the reaction, but is preferably 0.1 with respect to the metal atom involved in the polymerization reaction of the polymerization initiator. Molar equivalent or more, more preferably 0.3 molar equivalent or more. By setting it to 0.1 molar equivalent or more, the modification reaction can be sufficiently advanced, and the dispersibility of silica can be suitably improved.
　変性反応の温度は、通常、重合反応の温度と同じであり、－２０℃～１５０℃とすることが好ましく、０～１２０℃とすることがより好ましく、２０～１００℃とすることが特に好ましい。変性反応の温度が低いと、変性後の共役ジエン系重合体の粘度が上昇する傾向がある。一方、変性反応の温度が高いと、重合体が有する活性末端が失活しやすくなる。変性反応の反応時間は、好ましくは１分～５時間であり、より好ましくは２分～１時間である。反応溶液に含まれる共役ジエン系重合体を単離するには、例えばスチームストリッピング等の公知の脱溶媒方法及び熱処理等の乾燥の操作によって行うことができる。 The temperature of the modification reaction is usually the same as the temperature of the polymerization reaction, preferably −20 ° C. to 150 ° C., more preferably 0 to 120 ° C., and particularly preferably 20 to 100 ° C. . When the temperature of the modification reaction is low, the viscosity of the conjugated diene polymer after modification tends to increase. On the other hand, when the temperature of the modification reaction is high, the active terminal of the polymer tends to be deactivated. The reaction time of the denaturation reaction is preferably 1 minute to 5 hours, more preferably 2 minutes to 1 hour. Isolation of the conjugated diene polymer contained in the reaction solution can be carried out by a known solvent removal method such as steam stripping and a drying operation such as heat treatment.
・カップリング工程
　活性末端を有する変性共役ジエン系重合体につき、カップリング剤と反応させて、変性共役ジエン系重合体鎖の活性末端を不活性化することによって分子量を調整してもよい。カップリング剤としては、従来公知のものを使用でき、例えば、コハク酸アミド、フタル酸アミド、ジベンゾイルピリジン、ジブチルジクロロケイ素、メチルトリクロロケイ素、メチルジクロロケイ素、テトラクロロケイ素（四塩化ケイ素）、四臭化ケイ素、四ヨウ化ケイ素、トリクロロメトキシシラン、トリブロモメトキシシラン、トリメトキシシラン、メチルトリエトキシシラン、テトラメトキシシラン、テトラエトキシシラン、アジピン酸ジメチル、テレフタル酸ジメチル、テトラクロロスズ、テトラブロムスズ、トリクロロブチルスズ、トリクロロメチルスズ、トリクロロエチルスズ、トリクロロフェニルスズ、トリクロロオクチルスズ、ブチルスズトリスオクタノエート、ジブチルスズビスラウレート、エチレングリコールジグリシジルエーテル、トリクロルフォスフィン、無水ピロメリット酸、ジビニルベンゼン、トリクロロプロパン等が挙げられる。なお、カップリング剤は、これらの１種を単独で又は２種以上を組み合わせて使用することができる。 -Coupling step The modified conjugated diene polymer having an active end may be reacted with a coupling agent to inactivate the active end of the modified conjugated diene polymer chain to adjust the molecular weight. As the coupling agent, conventionally known coupling agents can be used. For example, succinic acid amide, phthalic acid amide, dibenzoylpyridine, dibutyldichlorosilicon, methyltrichlorosilicon, methyldichlorosilicon, tetrachlorosilicon (silicon tetrachloride), four Silicon bromide, silicon tetraiodide, trichloromethoxysilane, tribromomethoxysilane, trimethoxysilane, methyltriethoxysilane, tetramethoxysilane, tetraethoxysilane, dimethyl adipate, dimethyl terephthalate, tetrachlorotin, tetrabromotin , Trichlorobutyltin, trichloromethyltin, trichloroethyltin, trichlorophenyltin, trichlorooctyltin, butyltin trisoctanoate, dibutyltin bislaurate, ethylene glycol diglylate Jill ether, trichloromethyl phosphine, pyromellitic anhydride, divinylbenzene, trichloropropane, and the like. In addition, a coupling agent can be used individually by 1 type or in combination of 2 or more types.
　重合活性末端とカップリング剤との反応は、例えば溶液反応として行うことができる。カップリング剤の使用量は、重合開始剤が有する重合反応に関与する金属原子に対し、好ましくは０．１モル当量以上、より好ましくは０．３モル当量以上である。反応形式や反応温度、反応時間等の各種条件については末端変性工程の説明が適用される。 The reaction between the polymerization active terminal and the coupling agent can be performed, for example, as a solution reaction. The amount of the coupling agent used is preferably at least 0.1 molar equivalent, more preferably at least 0.3 molar equivalent, relative to the metal atom involved in the polymerization reaction of the polymerization initiator. The description of the terminal modification step is applied to various conditions such as reaction type, reaction temperature, and reaction time.
　本開示の変性共役ジエン系重合体の好ましい一つの態様としては、共役ジエン単位と芳香族ビニル単位とを有する共重合体鎖の両末端のそれぞれに共役ジエンブロックが結合されており、両末端の共役ジエンブロックのうち、一方の共役ジエンブロックが、１，３－ブタジエンを重合して形成されたブタジエンブロックであり、当該ブタジエンブロックにおいて共重合体鎖に結合していない側の末端に窒素含有基を有しており、他方の共役ジエンブロックが、共重合体鎖に結合していない側の末端にシリカと相互作用する官能基を有する重合体である。当該重合体によれば、得られる加硫ゴムにおける低燃費性能、耐摩耗性及びウェットグリップ性の改善効果が高く好適である。当該重合体は、直鎖状であっても分岐状であってもよい。 As a preferred embodiment of the modified conjugated diene polymer of the present disclosure, a conjugated diene block is bonded to each of both ends of a copolymer chain having a conjugated diene unit and an aromatic vinyl unit. Among the conjugated diene blocks, one conjugated diene block is a butadiene block formed by polymerizing 1,3-butadiene, and a nitrogen-containing group at the terminal of the butadiene block that is not bonded to the copolymer chain. And the other conjugated diene block is a polymer having a functional group that interacts with silica at the terminal not bonded to the copolymer chain. According to the polymer, the resulting vulcanized rubber is preferable because it has a high effect of improving fuel efficiency, wear resistance, and wet grip properties. The polymer may be linear or branched.
＜重合体組成物＞
　本開示の重合体組成物は、上記の変性共役ジエン系重合体を含むゴム成分、無機フィラー及び架橋剤を含有する。重合体組成物中における上記の変性共役ジエン系重合体の含有割合は、重合体組成物に含まれるゴム成分のうちの２０質量％以上であることが好ましく、３０質量％以上であることがより好ましく、４０質量％以上であることがさらに好ましい。ここで、無機フィラーとしては、シリカ及びカーボンブラックの少なくとも一方を好ましく使用できる。 <Polymer composition>
The polymer composition of the present disclosure contains a rubber component including the modified conjugated diene polymer, an inorganic filler, and a crosslinking agent. The content ratio of the modified conjugated diene polymer in the polymer composition is preferably 20% by mass or more of the rubber component contained in the polymer composition, and more preferably 30% by mass or more. Preferably, it is more preferably 40% by mass or more. Here, at least one of silica and carbon black can be preferably used as the inorganic filler.
　シリカとしては、例えば湿式シリカ（含水ケイ酸）、乾式シリカ（無水ケイ酸）、コロイダルシリカ、沈降シリカ、ケイ酸カルシウム、ケイ酸アルミニウム等が挙げられる。これらのうち、破壊特性の改良効果や、ウェットグリップ性と低転がり抵抗性との両立効果の観点から、湿式シリカが特に好ましい。また、高分散型（Ｈｉｇｈ　Ｄｉｓｐｅｒｓｉｂｌｅ　Ｔｙｐｅ）のシリカを使用することも、重合体組成物中における分散性を良好にできるとともに物性及び加工性を向上できる観点から好ましい。なお、シリカは、一種を単独で又は二種以上を組み合わせて用いることができる。 Examples of silica include wet silica (hydrous silicic acid), dry silica (anhydrous silicic acid), colloidal silica, precipitated silica, calcium silicate, and aluminum silicate. Among these, wet silica is particularly preferable from the viewpoint of the effect of improving fracture characteristics and the effect of achieving both wet grip properties and low rolling resistance. It is also preferable to use high dispersible type silica from the viewpoint of improving dispersibility in the polymer composition and improving physical properties and processability. In addition, a silica can be used individually by 1 type or in combination of 2 or more types.
　カーボンブラックとしては、ＧＰＦ、ＦＥＦ、ＨＡＦ、ＩＳＡＦ、ＳＡＦなどが挙げられるが、特に限定されるものではない。無機フィラーとしてカーボンブラックを使用することで、良好な補強効果が得られる。 Examples of carbon black include GPF, FEF, HAF, ISAF, and SAF, but are not particularly limited. By using carbon black as the inorganic filler, a good reinforcing effect can be obtained.
　重合体組成物には、フィラーとして、シリカやカーボンブラックの他に、クレー、炭酸カルシウムなどの各種の補強性充填剤が配合されていてもよい。重合体組成物中におけるシリカ及びカーボンブラックの合計量は、重合体組成物に含まれる重合体成分の全体量１００質量部に対して、好ましくは２０～１３０質量部、より好ましくは２５～１１０質量部である。 In the polymer composition, various reinforcing fillers such as clay and calcium carbonate may be blended as a filler in addition to silica and carbon black. The total amount of silica and carbon black in the polymer composition is preferably 20 to 130 parts by mass, more preferably 25 to 110 parts by mass with respect to 100 parts by mass of the total amount of the polymer components contained in the polymer composition. Part.
　架橋剤としては、硫黄、ハロゲン化硫黄、有機過酸化物、キノンジオキシム類、有機多価アミン化合物、メチロール基を有するアルキルフェノール樹脂等が挙げられ、通常、硫黄が使用される。硫黄の配合量は、重合体組成物に含まれる重合体成分の合計量１００質量部に対して、好ましくは０．１～５質量部、より好ましくは０．５～３質量部である。 Examples of the crosslinking agent include sulfur, sulfur halides, organic peroxides, quinonedioximes, organic polyvalent amine compounds, alkylphenol resins having a methylol group, and sulfur is usually used. The amount of sulfur is preferably 0.1 to 5 parts by mass, more preferably 0.5 to 3 parts by mass with respect to 100 parts by mass of the total amount of polymer components contained in the polymer composition.
　本開示の重合体組成物には、上記で得られた変性共役ジエン系重合体とは異なる他のゴム成分がさらに配合されていてもよい。かかる他のゴム成分の種類は特に限定されないが、ブタジエンゴム（ＢＲ、例えばシス－１，４結合９０％以上のハイシスＢＲ、シンジオタクチック－１，２－ポリブタジエン（ＳＰＢ）含有ＢＲなど）、スチレンブタジエンゴム（ＳＢＲ）、天然ゴム（ＮＲ）、イソプレンゴム（ＩＲ）、スチレンイソプレン共重合体ゴム、ブタジエンイソプレン共重合体ゴム等が挙げられる。他のゴム成分は、本開示の変性共役ジエン系重合体を用いたことによるヒステリシスロス低減及び耐摩耗性の改善効果が高い点で、変性又は未変性のＢＲ及びＳＢＲよりなる群から選ばれる少なくとも一種であることが好ましく、ウェットグリップ性及び加工性の改善効果が高い点で、ＮＲであることが好ましい。
　その他のゴム成分の配合量は、重合体組成物に含まれる重合体成分の合計量１００質量部に対して、好ましくは５～６０質量部、より好ましくは１０～５０質量部である。 Another rubber component different from the modified conjugated diene polymer obtained above may be further blended in the polymer composition of the present disclosure. The type of the other rubber component is not particularly limited, but butadiene rubber (BR, such as high cis BR having 90% or more of cis-1,4 bond, BR containing syndiotactic-1,2-polybutadiene (SPB), etc.), styrene Examples thereof include butadiene rubber (SBR), natural rubber (NR), isoprene rubber (IR), styrene isoprene copolymer rubber, and butadiene isoprene copolymer rubber. The other rubber component is at least selected from the group consisting of modified and unmodified BR and SBR in that the effect of reducing hysteresis loss and improving wear resistance is high by using the modified conjugated diene polymer of the present disclosure. It is preferable that it is 1 type, and it is preferable that it is NR at the point that the improvement effect of wet grip property and workability is high.
The blending amount of the other rubber components is preferably 5 to 60 parts by mass, more preferably 10 to 50 parts by mass with respect to 100 parts by mass of the total amount of the polymer components contained in the polymer composition.
　重合体組成物には、上記した成分の他に、例えば老化防止剤、亜鉛華、ステアリン酸、軟化剤、硫黄、加硫促進剤、シランカップリング剤、相溶化剤、加硫助剤、プロセスオイル、加工助剤、スコーチ防止剤など、タイヤ用ゴム組成物において一般に使用される各種添加剤を配合することができる。これらの配合割合は、本開示の効果を損なわない範囲で、各種成分に応じて適宜選択することができる。 In addition to the above-described components, the polymer composition includes, for example, anti-aging agent, zinc white, stearic acid, softener, sulfur, vulcanization accelerator, silane coupling agent, compatibilizer, vulcanization aid, process Various additives generally used in tire rubber compositions such as oil, processing aids, and scorch inhibitors can be blended. These blending ratios can be appropriately selected according to various components within a range not impairing the effects of the present disclosure.
　本開示の重合体組成物は、重合体成分、無機フィラー及び架橋剤の他、必要に応じて配合される成分を、開放式混練機（例えば、ロール）、密閉式混練機（例えば、バンバリーミキサー）等の混練機を用いて混練され、成形加工後に架橋（加硫）することによって、架橋物として各種ゴム製品に適用可能である。具体的には、例えばタイヤトレッド、アンダートレッド、カーカス、サイドウォール、ビード部等のタイヤ用途；パッキン、ガスケット、ウェザーストリップ、Ｏ－リング等のシール材；自動車、船舶、航空機、鉄道等の各種車両用の内外装表皮材；建築材料；産業機械用や設備用などの防振ゴム類；ダイヤフラム、ロール、ラジエータホース、エアーホース等の各種ホース及びホースカバー類；動力伝達用ベルトなどのベルト類；ライニング；ダストブーツ；医療用機器材料；防舷材；電線用絶縁材料；その他の工業品等の用途に適用できる。 In the polymer composition of the present disclosure, in addition to the polymer component, the inorganic filler, and the crosslinking agent, the components to be blended as necessary include an open kneader (for example, a roll) and a closed kneader (for example, a Banbury mixer). Etc.) and can be applied to various rubber products as a crosslinked product by crosslinking (vulcanizing) after molding. Specifically, for example, tire applications such as tire treads, under treads, carcass, sidewalls, and bead parts; seal materials such as packings, gaskets, weather strips, O-rings; various vehicles such as automobiles, ships, aircraft, and railways Interior and exterior skin materials for building; building materials; anti-vibration rubber for industrial machinery and equipment; various hoses and hose covers such as diaphragms, rolls, radiator hoses and air hoses; belts such as power transmission belts; Dust boots; Medical equipment materials; Fenders; Wire insulation materials; Other industrial products.
　本開示の製造方法によれば、ゴム組成物の加工性に優れ、また、低燃費性能、耐摩耗性及びウェットグリップ特性に優れた加硫ゴムを得ることができる変性共役ジエン系重合体を製造することができる。したがって、本開示の変性共役ジエン系重合体を含む重合体組成物は、特にタイヤのトレッド及びサイドウォール用の材料として好適に使用できる。 According to the production method of the present disclosure, a modified conjugated diene polymer is produced that is capable of obtaining a vulcanized rubber that is excellent in processability of the rubber composition and that is excellent in low fuel consumption performance, wear resistance, and wet grip characteristics. can do. Therefore, the polymer composition containing the modified conjugated diene polymer of the present disclosure can be suitably used particularly as a material for tire treads and sidewalls.
　タイヤの製造は常法に従い行うことができる。例えば、重合体組成物を混練機で混合し、シート状にしたものを、常法に従い所定位置に配して加硫成形することによりトレッドゴム又はサイドウォールゴムとして形成され、空気入りタイヤが得られる。 Tire production can be performed according to conventional methods. For example, a polymer composition is mixed in a kneader and formed into a sheet shape, and then placed at a predetermined position according to a conventional method and vulcanized to form a tread rubber or a sidewall rubber, thereby obtaining a pneumatic tire. It is done.
　以下、実施例に基づいて具体的に説明するが、本開示はこれらの実施例に限定されるものではない。なお、実施例、比較例中の「部」及び「％」は、特に断らない限り質量基準である。各種物性値の測定方法を以下に示す。 Hereinafter, although concretely described based on examples, the present disclosure is not limited to these examples. In the examples and comparative examples, “parts” and “%” are based on mass unless otherwise specified. The measuring method of various physical property values is shown below.
［重合体の特性評価］
・ビニル結合含量（％）：４００ＭＨｚの１Ｈ－ＮＭＲによって測定した。
・結合スチレン含量（％）：４００ＭＨｚの１Ｈ－ＮＭＲ測定によって測定した。
・変性前の重量平均分子量（変性反応前ピーク分子量）：以下の測定条件で、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）（Ｖｉｓｃｏｔｅｋ　ＴＤＡ３０２（商品名（Ｖｉｓｃｏｔｅｋ社製）））を使用して得られたＧＰＣ曲線につき、分子量が最も小さいピークの頂点に相当する保持時間からポリスチレン換算で求めた。
（ＧＰＣ測定条件）
　　カラム：商品名「ＴＳＫ　ｇｅｌ　ＨＨＲ－Ｈ」（東ソー社製）２本
　　カラム温度：４０℃
　　移動相：テトラヒドロフラン
　　流速：１．０ｍｌ／分
　　サンプル濃度：１０ｍｇ／２０ｍｌ
・ムーニー粘度（ＭＬ１＋４，１００℃）：ＪＩＳ　Ｋ６３００－１：２０１３に準拠し、Ｌローターを使用して、予熱１分、ローター作動時間４分、温度１００℃の条件で求めた。 [Evaluation of polymer properties]
Vinyl bond content (%): measured by 1 H-NMR at 400 MHz.
Bonded styrene content (%): Measured by 1 H-NMR measurement at 400 MHz.
Weight average molecular weight before denaturation (peak molecular weight before denaturation reaction): GPC obtained using gel permeation chromatography (GPC) (Viscotek TDA302 (trade name (manufactured by Viscotek))) under the following measurement conditions. The curve was calculated in terms of polystyrene from the retention time corresponding to the peak peak with the smallest molecular weight.
(GPC measurement conditions)
Column: Two brand names “TSK gel HHR-H” (manufactured by Tosoh Corporation) Column temperature: 40 ° C.
Mobile phase: Tetrahydrofuran Flow rate: 1.0 ml / min Sample concentration: 10 mg / 20 ml
Mooney viscosity (ML 1 + 4 , 100 ° C.): Determined according to JIS K6300-1: 2013, using an L rotor under conditions of preheating 1 minute, rotor operating time 4 minutes, temperature 100 ° C.
（合成例１：変性共役ジエン開始剤Ａの合成）
　窒素置換された内容積０．５リットルのガラス瓶反応器に、Ｎ－トリメチルシリルピペラジン５．４２ｍｍｏｌ、シクロヘキサン５０ｇ、テトラヒドロフラン５ｇ、ｎ－ブチルリチウム７．００ｍｍｏｌを仕込んだ。反応器内容物の温度を２０℃に調整した後、１，３－ブタジエン６.３ｇを５分間かけて添加し重合を行い、変性共役ジエン開始剤Ａを得た。 (Synthesis Example 1: Synthesis of Modified Conjugated Diene Initiator A)
A glass bottle reactor purged with nitrogen and having an internal volume of 0.5 liter was charged with 5.42 mmol of N-trimethylsilylpiperazine, 50 g of cyclohexane, 5 g of tetrahydrofuran, and 7.00 mmol of n-butyllithium. After adjusting the temperature of the reactor contents to 20 ° C., 6.3 g of 1,3-butadiene was added over 5 minutes for polymerization to obtain a modified conjugated diene initiator A.
（合成例２：変性共役ジエン開始剤Ｂの合成）
　Ｎ－トリメチルシリルピペラジンをピペリジンに替えた以外は合成例１と同様の操作で変性共役ジエン開始剤Ｂを得た。
（合成例３：変性低分子共役ジエン系開始剤Ｃの合成）
　Ｎ－トリメチルシリルピペラジンをジイソブチルアミンに替えた以外は合成例１と同様の操作で変性共役ジエン開始剤Ｃを得た。 (Synthesis Example 2: Synthesis of Modified Conjugated Diene Initiator B)
A modified conjugated diene initiator B was obtained in the same manner as in Synthesis Example 1 except that N-trimethylsilylpiperazine was replaced with piperidine.
(Synthesis Example 3: Synthesis of Modified Low Molecular Conjugated Diene Initiator C)
A modified conjugated diene initiator C was obtained in the same manner as in Synthesis Example 1 except that N-trimethylsilylpiperazine was replaced with diisobutylamine.
［実施例１－１：変性共役ジエン系ゴムＢの合成］
　窒素置換された内容積５リットルのオートクレーブ反応器に、シクロヘキサン２４５０ｇ、２，２－ジ（２－テトラヒドロフリル）プロパン３．３７ｍｍｏｌ、スチレン１７０ｇ、１，３－ブタジエン４２２ｇを仕込んだ。反応器内容物の温度を１０℃に調整した後、重合開始剤として変性共役ジエン開始剤Ａをリチウム７．００ｍｍｏｌ分添加して重合を開始した。重合は断熱条件で実施し、最高温度は８５℃に達した。重合転化率が９９％に達した時点（重合開始から１９分経過後）で、１，３－ブタジエン３０ｇを５分間かけて追加し、更に３分間重合させた後、Ｎ，Ｎ－ビス（トリメチルシリル）アミノプロピルメチルジエトキシシラン５．４２ｍｍｏｌを加えて１５分間反応を行って、変性共役ジエン系重合体を含む重合体溶液を得た。
　得られた変性共役ジエン系重合体を含む重合体溶液に、２，６－ジ－ｔｅｒｔ－ブチル－４－メチル－フェノールを添加し、次いで、スチームストリッピングにより脱溶媒を行い、１１０℃に調温された熱ロールで乾燥することにより変性共役ジエン系ゴムＢを得た。変性共役ジエン系ゴムＢの重合処方を下記表１に、得られた変性共役ジエン系ゴムＢの性質を下記表２に示す。 [Example 1-1: Synthesis of modified conjugated diene rubber B]
An autoclave reactor with an internal volume of 5 liters purged with nitrogen was charged with 2450 g of cyclohexane, 3.37 mmol of 2,2-di (2-tetrahydrofuryl) propane, 170 g of styrene and 422 g of 1,3-butadiene. After adjusting the temperature of the reactor contents to 10 ° C., 7.00 mmol of modified conjugated diene initiator A as a polymerization initiator was added to initiate polymerization. The polymerization was carried out under adiabatic conditions and the maximum temperature reached 85 ° C. When the polymerization conversion rate reached 99% (after 19 minutes from the start of polymerization), 30 g of 1,3-butadiene was added over 5 minutes, and after further polymerization for 3 minutes, N, N-bis (trimethylsilyl) was added. ) Aminopropylmethyldiethoxysilane (5.42 mmol) was added and reacted for 15 minutes to obtain a polymer solution containing a modified conjugated diene polymer.
2,6-Di-tert-butyl-4-methyl-phenol is added to the resulting polymer solution containing the modified conjugated diene polymer, and then the solvent is removed by steam stripping to adjust the temperature to 110 ° C. The modified conjugated diene rubber B was obtained by drying with a heated hot roll. The polymerization formulation of the modified conjugated diene rubber B is shown in Table 1 below, and the properties of the resulting modified conjugated diene rubber B are shown in Table 2 below.
［実施例１－２，１－３］
　使用する重合開始剤の種類を、実施例１－２については変性共役ジエン開始剤Ｂに変更し、実施例１－３については変性共役ジエン開始剤Ｃに変更した点以外は実施例１－１と同様の方法により変性共役ジエン系ゴムＣ，Ｄをそれぞれ得た（下記表１参照）。なお、変性共役ジエン開始剤Ｂ、変性共役ジエン開始剤Ｃの配合量は、実施例１－１と同様、リチウム７ｍｍｏｌ分とした。得られた変性共役ジエン系ゴムＣ，Ｄの性質を下記表２に示す。 [Examples 1-2 and 1-3]
The type of polymerization initiator used was changed to Example 1-1, except that Example 1-2 was changed to modified conjugated diene initiator B, and Example 1-3 was changed to modified conjugated diene initiator C. Modified conjugated diene rubbers C and D were obtained in the same manner as described above (see Table 1 below). The blending amount of the modified conjugated diene initiator B and the modified conjugated diene initiator C was set to 7 mmol of lithium as in Example 1-1. The properties of the resulting modified conjugated diene rubbers C and D are shown in Table 2 below.
［比較例１－１：変性共役ジエン系ゴムＥの合成］
　窒素置換された内容積５リットルのオートクレーブ反応器に、Ｎ－（ｔｅｒｔ－ブチルジメチルシリル）ピペラジン５．４２ｍｍｏｌ、シクロヘキサン２５００ｇ、テトラヒドロフラン５ｇ、スチレン１７０ｇ、１，３－ブタジエン４２８ｇを仕込んだ。反応器内容物の温度を１０℃に調整した後、ｎ－ブチルリチウム７．００ｍｍｏｌを添加して重合を開始した。重合は断熱条件で実施し、最高温度は８５℃に達した。重合転化率が９９％に達した時点（重合開始から２６分経過後）で、１，３－ブタジエン３０ｇを５分間かけて追加し、更に、３分間重合させた後、Ｎ，Ｎ－ビス（トリメチルシリル）アミノプロピルメチルジエトキシシラン５．４２ｍｍｏｌを加えて１５分間反応を行って、共役ジエン系重合体を含む重合体溶液を得た。
　得られた共役ジエン系重合体を含む重合体溶液に、２，６－ジ－ｔｅｒｔ－ブチル－４－メチル－フェノールを添加し、次いで、スチームストリッピングにより脱溶媒を行い、１１０℃に調温された熱ロールで乾燥することにより変性共役ジエン系ゴムＥを得た。変性共役ジエン系ゴムＥの重合処方を下記表１に、得られた変性共役ジエン系ゴムＥの性質を下記表２に示す。 [Comparative Example 1-1: Synthesis of Modified Conjugated Diene Rubber E]
An autoclave reactor with an internal volume of 5 liters purged with nitrogen was charged with 5.42 mmol of N- (tert-butyldimethylsilyl) piperazine, 2500 g of cyclohexane, 5 g of tetrahydrofuran, 170 g of styrene, and 428 g of 1,3-butadiene. After adjusting the temperature of the reactor contents to 10 ° C., 7.00 mmol of n-butyllithium was added to initiate polymerization. The polymerization was carried out under adiabatic conditions and the maximum temperature reached 85 ° C. When the polymerization conversion rate reached 99% (26 minutes after the start of polymerization), 30 g of 1,3-butadiene was added over 5 minutes, and after further polymerization for 3 minutes, N, N-bis ( Trimethylsilyl) aminopropylmethyldiethoxysilane (5.42 mmol) was added and reacted for 15 minutes to obtain a polymer solution containing a conjugated diene polymer.
2,6-Di-tert-butyl-4-methyl-phenol is added to the resulting polymer solution containing the conjugated diene polymer, and then the solvent is removed by steam stripping, and the temperature is adjusted to 110 ° C. The modified conjugated diene rubber E was obtained by drying with a heated roll. The polymerization formulation of the modified conjugated diene rubber E is shown in Table 1 below, and the properties of the resulting modified conjugated diene rubber E are shown in Table 2 below.
［比較例１－２］
　Ｎ－（ｔｅｒｔ－ブチルジメチルシリル）ピペラジンに替えてピペリジンを使用した点以外は比較例１－１と同様の方法により変性共役ジエン系ゴムＦを得た。得られた変性共役ジエン系ゴムＦの性質を下記表２に示す。 [Comparative Example 1-2]
A modified conjugated diene rubber F was obtained in the same manner as in Comparative Example 1-1 except that piperidine was used instead of N- (tert-butyldimethylsilyl) piperazine. The properties of the resulting modified conjugated diene rubber F are shown in Table 2 below.
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
　表１中、変性共役ジエン開始剤Ａ～Ｃの数値は、各開始剤が有するリチウムの量（ｍｍｏｌ）を表す。なお、表１には、変性共役ジエン開始剤Ａ～Ｃをそれぞれ「開始剤Ａ～Ｃ」と記載した。化合物の略称は以下の通りである。
　ＤＴＨＦＰ（＊１）；２，２－ジ（２－テトラヒドロフリル）プロパン
　ＩＮＩ－Ｎ－２（＊２）；Ｎ－（ｔｅｒｔ－ブチルジメチルシリル）ピペラジン
　ＩＮＩ－Ｎ－３（＊３）；ピペリジン
　Ｎ－Ｓｉ－１（＊４）；Ｎ，Ｎ－ビス（トリメチルシリル）アミノプロピルメチルジエトキシシラン
　ＢＨＴ（＊５）；２，６－ジ－ｔｅｒｔ－ブチル－４－メチル－フェノール In Table 1, the numerical values of the modified conjugated diene initiators A to C represent the amount (mmol) of lithium that each initiator has. In Table 1, the modified conjugated diene initiators A to C are indicated as “initiators A to C”, respectively. Abbreviations of the compounds are as follows.
DTHP (* 1); 2,2-di (2-tetrahydrofuryl) propane INI-N-2 (* 2); N- (tert-butyldimethylsilyl) piperazine INI-N-3 (* 3); piperidine N -Si-1 (* 4); N, N-bis (trimethylsilyl) aminopropylmethyldiethoxysilane BHT (* 5); 2,6-di-tert-butyl-4-methyl-phenol
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
［実施例２－１：ゴム組成物の調製及び物性評価］
　変性共役ジエン系ゴムＢを用いて、下記表３に示す配合処方により調製したゴム組成物を加硫して物性評価を行った。ゴム組成物の混練方法及び評価方法は以下の通りである。・ゴム組成物の混練り方法及び評価方法
　温度制御装置が付属されたプラストミル（内容量２５０ｃｃ）を使用し、一段目の混練として、充填率７２％、回転数６０ｒｐｍの条件で、ゴム成分、シリカ、カーボンブラック、シランカップリング剤、ステアリン酸、老化防止剤、酸化亜鉛を混練した。なお、実施例２－１では、ゴム成分として変性共役ジエン系ゴムＢを７０質量部、ブタジエンゴム（ＢＲ０１、ＪＳＲ株式会社製）を３０質量部使用した（下記表４参照）。次いで、二段目の混練として、上記で得た配合物を室温まで冷却後、硫黄、加硫促進剤を加えて混練した。これを成型し、１６０℃で所定時間、加硫プレスにて加硫し、以下のタイヤ性能を表す特性評価を実施した。
（ｉ）ムーニー粘度：加硫前のゴム組成物を測定用試料とし、ＪＩＳ　Ｋ６３００－１：２０１３に準拠し、Ｌローターを使用して、予熱１分、ローター作動時間４分、温度１００℃の条件で測定した。ムーニー粘度が小さいほど加工性が良好である。
（ｉｉ）０℃ｔａｎδ：加硫ゴムを測定用試料とし、動的スペクトロメーター（米国レオメトリックス社製）を使用し、引張動歪０．１４％、角速度１００ラジアン毎秒、０℃の条件で測定した。比較例２－１を１００とした指数で表示し、数値が大きいほどウェットスキッド抵抗性が大きくウェットグリップ特性が良好である。
（ｉｉｉ）７０℃ｔａｎδ：加硫ゴムを測定用試料とし、動的スペクトロメーター（米国レオメトリックス社製）を使用し、引張動歪０．７％、角速度１００ラジアン毎秒、７０℃の条件で測定した。比較例２－１を１００とした指数で表示し、数値が大きいほどヒステリシスロスが小さく低燃費性能が良好である。
（ｉｖ）耐摩耗性：加硫ゴムを測定用試料とし、ＤＩＮ摩耗試験機（東洋精機社製）を使用し、ＪＩＳ　Ｋ　６２６４－２：２００５に準拠し、荷重１０Ｎで２５℃にて測定した。比較例２－１を１００とした指数で表示し、数値が大きいほど耐摩耗性が良好である。
　物性評価の結果を下記表５に示す。 [Example 2-1: Preparation of rubber composition and evaluation of physical properties]
Using the modified conjugated diene rubber B, the rubber composition prepared according to the formulation shown in Table 3 below was vulcanized to evaluate the physical properties. The kneading method and evaluation method of the rubber composition are as follows.・ Kneading method and evaluation method of rubber composition Using a plastmill (with an internal volume of 250 cc) equipped with a temperature control device, as a first-stage kneading, under conditions of a filling rate of 72% and a rotational speed of 60 rpm, a rubber component, silica Carbon black, silane coupling agent, stearic acid, anti-aging agent, and zinc oxide were kneaded. In Example 2-1, 70 parts by mass of modified conjugated diene rubber B and 30 parts by mass of butadiene rubber (BR01, manufactured by JSR Corporation) were used as rubber components (see Table 4 below). Next, as the second stage kneading, the blend obtained above was cooled to room temperature, and then sulfur and a vulcanization accelerator were added and kneaded. This was molded and vulcanized with a vulcanizing press at 160 ° C. for a predetermined time, and the characteristic evaluation representing the following tire performance was performed.
(I) Mooney viscosity: A rubber composition before vulcanization was used as a measurement sample, and in accordance with JIS K6300-1: 2013, using an L rotor, preheating was 1 minute, rotor operation time was 4 minutes, and temperature was 100 ° C. Measured under conditions. The smaller the Mooney viscosity, the better the processability.
(Ii) 0 ° C. tan δ: Measured using a vulcanized rubber as a measurement sample and using a dynamic spectrometer (manufactured by Rheometrics, USA) under conditions of tensile dynamic strain of 0.14%, angular velocity of 100 radians per second, and 0 ° C. did. Expressed as an index with Comparative Example 2-1 as 100, the larger the value, the greater the wet skid resistance and the better the wet grip characteristics.
(Iii) 70 [deg.] C. tan [delta]: measured using vulcanized rubber as a measurement sample and using a dynamic spectrometer (manufactured by Rheometrics, USA) under conditions of a tensile dynamic strain of 0.7%, an angular velocity of 100 radians per second, and 70 [deg.] C. did. Displayed as an index with Comparative Example 2-1 as 100, the larger the value, the smaller the hysteresis loss and the better the fuel efficiency.
(Iv) Abrasion resistance: measured with a vulcanized rubber as a measurement sample and using a DIN abrasion tester (manufactured by Toyo Seiki Co., Ltd.) according to JIS K 6264-2: 2005 at a load of 10 N at 25 ° C. . Expressed as an index with Comparative Example 2-1 as 100, the larger the value, the better the wear resistance.
The results of physical property evaluation are shown in Table 5 below.
［実施例２－２～２－６、比較例２－１～２－６］
　使用するゴム成分の種類及び量を下記表４に記載の通り変更した点以外は実施例２－１と同様にしてゴム組成物を調製し、調製したゴム組成物を加硫して物性評価を行った。物性評価の結果を下記表５及び表６に示す。 [Examples 2-2 to 2-6, Comparative Examples 2-1 to 2-6]
A rubber composition was prepared in the same manner as in Example 2-1, except that the types and amounts of the rubber components used were changed as shown in Table 4 below, and the prepared rubber composition was vulcanized to evaluate physical properties. went. The results of physical property evaluation are shown in Tables 5 and 6 below.
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000006
　表３中、各成分について、使用した商品名は以下の通りである。
＊１；ローディア社製　ＺＥＯＳＩＬ　１１６５ＭＰ
＊２；三菱化学社製　ダイアブラックＮ３３９
＊３；エボニック社製　Ｓｉ７５
＊４；住友化学社製　スミライザーＧＭ
＊５；大内新興化学工業社製　ノクラックＮＳ－１０
＊６；大内新興化学工業社製　ノクセラーＤ
＊７；大内新興化学工業社製　ノクセラーＣＺ In Table 3, the trade names used for each component are as follows.
* 1; ZEOSIL 1165MP manufactured by Rhodia
* 2: Dia Black N339 manufactured by Mitsubishi Chemical Corporation
* 3: E75 Si75
* 4 Sumitizer GM manufactured by Sumitomo Chemical Co., Ltd.
* 5: Nocrack NS-10 manufactured by Ouchi Shinsei Chemical Co., Ltd.
* 6: Noxeller D manufactured by Ouchi Shinsei Chemical Industry Co., Ltd.
* 7: Noxeller CZ manufactured by Ouchi Shinsei Chemical Industry Co., Ltd.
Figure JPOXMLDOC01-appb-T000007
Figure JPOXMLDOC01-appb-T000007
　表４中のゴム成分の略称につき、使用した商品名は以下の通りである。
Ｌ；ブタジエンゴム（商品名ＢＲ０１、ＪＳＲ株式会社製）
ＮＲ；天然ゴム　ＲＳＳ－３号 The trade names used for the abbreviations of the rubber components in Table 4 are as follows.
L: Butadiene rubber (trade name BR01, manufactured by JSR Corporation)
NR: Natural rubber RSS-3
Figure JPOXMLDOC01-appb-T000008
Figure JPOXMLDOC01-appb-T000008
Figure JPOXMLDOC01-appb-T000009
Figure JPOXMLDOC01-appb-T000009
　表５及び表６に示すように、実施例２－１～２－６によって得られた変性共役ジエン系ゴムは、比較例で得られた変性共役ジエン系ゴムに比べて、ゴム組成物の加工性、並びに加硫ゴムの低燃費性能、耐摩耗性及びウェットグリップ性のバランスが取れていた。
　また、ゴム成分のうちその他のゴムとしてＢＲを用いた実施例２－１，２－４は、ＮＲを用いた実施例２－３，２－６よりもヒステリシスロス及び耐摩耗性の改良幅が大きく、ＮＲを用いた実施例２－３，２－６は、ＢＲを用いた実施例２－１，２－４よりもウェットグリップ特性の改良幅が大きかった。 As shown in Tables 5 and 6, the modified conjugated diene rubbers obtained in Examples 2-1 to 2-6 are more processed than the modified conjugated diene rubbers obtained in Comparative Examples. And the low fuel consumption performance, wear resistance, and wet grip properties of the vulcanized rubber were balanced.
In addition, Examples 2-1 and 2-4 using BR as other rubber among the rubber components have improved hysteresis loss and abrasion resistance widths than Examples 2-3 and 2-6 using NR. Largely, Examples 2-3 and 2-6 using NR had a greater improvement in wet grip characteristics than Examples 2-1 and 2-4 using BR.
　以上のことから、ブタジエンブロックを有する変性共役ジエン開始剤を用いて得られる変性共役ジエン系重合体によれば、ゴム組成物の加工性に優れ、しかも低燃費性能、耐摩耗性及びウェットグリップ特性に優れた加硫ゴムを得ることができることが確認された。 From the above, according to the modified conjugated diene polymer obtained by using the modified conjugated diene initiator having a butadiene block, the rubber composition is excellent in processability and has low fuel consumption performance, wear resistance and wet grip characteristics. It was confirmed that an excellent vulcanized rubber can be obtained.

Claims (15)

  1. 　水素原子が結合した窒素原子を有する窒素含有化合物Ｘと、アルカリ金属化合物及びアルカリ土類金属化合物の少なくともいずれかの金属化合物Ｙとを混合して得られる化合物の存在下で１，３－ブタジエンを重合する工程Ａと、
    　前記工程Ａで得られた重合体の存在下で、共役ジエン化合物及び芳香族ビニル化合物を重合する工程Ｂと、を含む変性共役ジエン系重合体の製造方法。     1,3-butadiene in the presence of a compound obtained by mixing a nitrogen-containing compound X having a nitrogen atom to which a hydrogen atom is bonded and at least one of an alkali metal compound and an alkaline earth metal compound. Polymerization step A;
    A process B for polymerizing a conjugated diene compound and an aromatic vinyl compound in the presence of the polymer obtained in the process A, and a method for producing a modified conjugated diene polymer.
  2. 　前記金属化合物Ｙが、リチウム化合物又はナトリウム化合物である、請求項１に記載の変性共役ジエン系重合体の製造方法。 The method for producing a modified conjugated diene polymer according to claim 1, wherein the metal compound Y is a lithium compound or a sodium compound.
  3. 　前記窒素含有化合物Ｘが環状アミン化合物である、請求項１又は２に記載の変性共役ジエン系重合体の製造方法。 The method for producing a modified conjugated diene polymer according to claim 1 or 2, wherein the nitrogen-containing compound X is a cyclic amine compound.
  4. 　前記窒素含有化合物Ｘの使用割合が、前記金属化合物Ｙの１モルに対して０．１～１０モルである、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の製造方法。 The production of the modified conjugated diene polymer according to any one of claims 1 to 3, wherein a use ratio of the nitrogen-containing compound X is 0.1 to 10 moles with respect to 1 mole of the metal compound Y. Method.
  5. 　前記工程Ａの１，３－ブタジエンの重合における１，３－ブタジエンの使用割合が、前記工程Ｂの共役ジエン化合物及び芳香族ビニル化合物の重合で使用する共役ジエン化合物と芳香族ビニル化合物との合計量に対して０．１～５質量％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の製造方法。 The proportion of 1,3-butadiene used in the polymerization of 1,3-butadiene in the step A is the sum of the conjugated diene compound and the aromatic vinyl compound used in the polymerization of the conjugated diene compound and the aromatic vinyl compound in the step B. The process for producing a modified conjugated diene polymer according to any one of claims 1 to 4, wherein the content is 0.1 to 5% by mass based on the amount.
  6. 　前記工程Ｂにおいて、共役ジエン化合物及び芳香族ビニル化合物の重合後に共役ジエン化合物を更に重合して、重合終了末端に共役ジエンブロックを形成する、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の製造方法。 The modification according to any one of claims 1 to 5, wherein, in the step B, the conjugated diene compound and the aromatic vinyl compound are further polymerized and then the conjugated diene compound is further polymerized to form a conjugated diene block at the terminal end of the polymerization. A method for producing a conjugated diene polymer.
  7. 　前記工程Ｂで重合終了末端に形成される共役ジエンブロックは、１，３－ブタジエンを重合して形成されるブタジエンブロックである、請求項６に記載の変性共役ジエン系重合体の製造方法。 The method for producing a modified conjugated diene polymer according to claim 6, wherein the conjugated diene block formed at the end of polymerization in the step B is a butadiene block formed by polymerizing 1,3-butadiene.
  8. 　前記金属化合物Ｙの使用割合が、前記工程Ａの重合で使用する１，３－ブタジエン１００ｇに対して１０～２０００ｍｍｏｌである、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の製造方法。 The modified conjugated diene heavy polymer according to any one of claims 1 to 7, wherein the metal compound Y is used in an amount of 10 to 2000 mmol based on 100 g of 1,3-butadiene used in the polymerization in the step A. Manufacturing method of coalescence.
  9. 　前記工程Ｂにより活性末端を有する重合体を得て、
    　前記工程Ｂで得られた活性末端を有する重合体と、シリカと相互作用する官能基を有し且つ前記活性末端と反応し得る化合物と、を反応させる工程を更に含む、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。     Obtaining a polymer having an active end by the step B,
    The method further comprises a step of reacting the polymer having an active end obtained in the step B with a compound having a functional group capable of interacting with silica and capable of reacting with the active end. The manufacturing method of the modified | denatured conjugated diene type polymer as described in any one.
  10. 　前記工程Ｂにより活性末端を有する重合体を得て、
    　前記工程Ｂで得られた活性末端を有する重合体と、カップリング剤とを反応させる工程を更に含む、請求項１～９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。     Obtaining a polymer having an active end by the step B,
    The method for producing a modified conjugated diene polymer according to any one of claims 1 to 9, further comprising a step of reacting the polymer having an active end obtained in the step B with a coupling agent.
  11. 　共役ジエン単位と芳香族ビニル単位とを有する共重合体鎖の両末端に、共役ジエン化合物を重合して形成された共役ジエンブロックがそれぞれ結合されており、かつ、
    　一方の前記共役ジエンブロックが、１，３－ブタジエンを重合して形成されたブタジエンブロックであり、前記共重合体鎖に結合していない側の末端に窒素含有基を有し、
    　他方の前記共役ジエンブロックが、前記共重合体鎖に結合していない側の末端にシリカと相互作用する官能基を有する、変性共役ジエン系重合体。     A conjugated diene block formed by polymerizing a conjugated diene compound is bonded to both ends of a copolymer chain having a conjugated diene unit and an aromatic vinyl unit, and
    One of the conjugated diene blocks is a butadiene block formed by polymerizing 1,3-butadiene, and has a nitrogen-containing group at the terminal not bonded to the copolymer chain,
    The modified conjugated diene-based polymer, wherein the other conjugated diene block has a functional group that interacts with silica at the terminal that is not bonded to the copolymer chain.
  12. 　１，３－ブタジエンを重合して形成されたブタジエンブロックの一方の末端に窒素含有基を有し、他方の末端が活性末端である重合体鎖の存在下で、共役ジエン化合物及び芳香族ビニル化合物を重合して得られる変性共役ジエン系重合体。 A conjugated diene compound and an aromatic vinyl compound in the presence of a polymer chain having a nitrogen-containing group at one end of a butadiene block formed by polymerizing 1,3-butadiene and the other end being an active end Modified conjugated diene polymer obtained by polymerizing
  13. 　請求項１～１０のいずれか一項に記載の製造方法により得られる変性共役ジエン系重合体、又は請求項１１若しくは請求項１２に記載の変性共役ジエン系重合体と、無機フィラーと、架橋剤とを含む重合体組成物。 A modified conjugated diene polymer obtained by the production method according to any one of claims 1 to 10, or a modified conjugated diene polymer according to claim 11 or 12, an inorganic filler, and a crosslinking agent A polymer composition comprising:
  14. 　請求項１３に記載の重合体組成物を架橋させてなる架橋物。 A cross-linked product obtained by cross-linking the polymer composition according to claim 13.
  15. 　請求項１４に記載の架橋物を用いて形成されたタイヤ。 A tire formed using the cross-linked product according to claim 14.
PCT/JP2017/041264 2016-11-16 2017-11-16 Modified conjugate diene-based polymer production method, modified conjugate diene-based polymer, polymer composition, crosslinked product, and tire WO2018092843A1 (en)

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