WO2018092843A1 - Procédé de production de polymère à base de diène conjugué modifié, polymère à base de diène conjugué modifié, composition polymère, produit réticulé, et pneu - Google Patents

Procédé de production de polymère à base de diène conjugué modifié, polymère à base de diène conjugué modifié, composition polymère, produit réticulé, et pneu 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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English (en)
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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    • 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.

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Abstract

La présente invention concerne un polymère à base de diène conjugué modifié qui est produit par un procédé de production qui comprend : une étape A consistant à polymériser du 1,3-butadiène en présence d'un composé obtenu par mélange d'un composé X contenant de l'azote comportant un atome d'azote auquel est lié un atome d'hydrogène et d'un composé métallique Y qui est un composé de métal alcalin et/ou un composé de métal alcalino-terreux ; et une étape B consistant à polymériser un composé conjugué et un composé vinylique aromatique en présence du polymère obtenu lors de l'étape A.
PCT/JP2017/041264 2016-11-16 2017-11-16 Procédé de production de polymère à base de diène conjugué modifié, polymère à base de diène conjugué modifié, composition polymère, produit réticulé, et pneu WO2018092843A1 (fr)

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06206920A (ja) * 1992-10-02 1994-07-26 Bridgestone Corp 可溶化されたアニオン重合開始剤及びそれらからの生成物
US20070173612A1 (en) * 2002-08-01 2007-07-26 Bridgestone Firestone Multi-functional polymers
WO2011105362A1 (fr) * 2010-02-26 2011-09-01 日本ゼオン株式会社 Caoutchouc diène conjugué, composition de caoutchouc, caoutchouc réticulé, pneu et procédé de fabrication d'un caoutchouc diène conjugué
WO2012086496A1 (fr) * 2010-12-24 2012-06-28 日本ゼオン株式会社 Caoutchouc de diène conjugué, composition de caoutchouc, produit réticulé de caoutchouc et pneu
WO2013094629A1 (fr) * 2011-12-23 2013-06-27 Jsr株式会社 Polymère diène conjugué modifié et son procédé de production
WO2015064646A1 (fr) * 2013-10-31 2015-05-07 Jsr株式会社 Caoutchouc réticulé, élément pour pneus, élément anti-vibrations, élément pour nappe d'armature, et composition de caoutchouc
JP2016037543A (ja) * 2014-08-07 2016-03-22 日本ゼオン株式会社 共役ジエン系ゴムの製造方法

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06206920A (ja) * 1992-10-02 1994-07-26 Bridgestone Corp 可溶化されたアニオン重合開始剤及びそれらからの生成物
US20070173612A1 (en) * 2002-08-01 2007-07-26 Bridgestone Firestone Multi-functional polymers
WO2011105362A1 (fr) * 2010-02-26 2011-09-01 日本ゼオン株式会社 Caoutchouc diène conjugué, composition de caoutchouc, caoutchouc réticulé, pneu et procédé de fabrication d'un caoutchouc diène conjugué
WO2012086496A1 (fr) * 2010-12-24 2012-06-28 日本ゼオン株式会社 Caoutchouc de diène conjugué, composition de caoutchouc, produit réticulé de caoutchouc et pneu
WO2013094629A1 (fr) * 2011-12-23 2013-06-27 Jsr株式会社 Polymère diène conjugué modifié et son procédé de production
WO2015064646A1 (fr) * 2013-10-31 2015-05-07 Jsr株式会社 Caoutchouc réticulé, élément pour pneus, élément anti-vibrations, élément pour nappe d'armature, et composition de caoutchouc
JP2016037543A (ja) * 2014-08-07 2016-03-22 日本ゼオン株式会社 共役ジエン系ゴムの製造方法

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