WO2021020189A1 - Composition polymère, polymère réticulé et pneumatique - Google Patents

Composition polymère, polymère réticulé et pneumatique Download PDF

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Publication number
WO2021020189A1
WO2021020189A1 PCT/JP2020/027997 JP2020027997W WO2021020189A1 WO 2021020189 A1 WO2021020189 A1 WO 2021020189A1 JP 2020027997 W JP2020027997 W JP 2020027997W WO 2021020189 A1 WO2021020189 A1 WO 2021020189A1
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group
thio
polymer
carbon atoms
conjugated diene
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PCT/JP2020/027997
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English (en)
Japanese (ja)
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倫子 真下
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Jsr株式会社
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Publication of WO2021020189A1 publication Critical patent/WO2021020189A1/fr

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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
    • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
    • C08C4/00—Treatment of rubber before vulcanisation, not provided for in groups C08C1/00 - C08C3/02
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
    • Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction 

Definitions

  • the present invention relates to a polymer composition, a crosslinked polymer, and a tire produced by using the crosslinked polymer.
  • Patent Document 1 discloses that when this material is used as a tread material for a tire, it is excellent in heat generation, wear resistance, and wet grip.
  • Patent Document 1 when the modified conjugated diene polymer disclosed in Patent Document 1 is used as a tread material for a tire, the dispersibility of fillers such as carbon black and silica contained in the polymer composition is not very good, and the polymer is broken. There is a problem that it is difficult to obtain sufficient performance in terms of strength and wear resistance.
  • some aspects of the present invention provide a polymer composition suitable for producing a tire which has good workability and is highly balanced in breaking strength and wear resistance. In addition, some aspects of the present invention provide a tire that is highly balanced in breaking strength and wear resistance.
  • the present invention has been made to solve at least a part of the above-mentioned problems, and can be realized as the following aspects.
  • One aspect of the polymer composition according to the present invention is (A) A polymer of a conjugated diene compound or a copolymer of a conjugated diene compound and an aromatic vinyl compound, which comprises an active polymerization terminal and a compound represented by any of the following general formulas (1) to (4). Conjugated diene-based polymer, which is a reactant, (B) Carbon black having a nitrogen adsorption specific surface area (N 2 SA) of 75 m 2 / g or more and 130 m 2 / g or less. Contains, The carbon black (B) is contained in an amount of 30 parts by mass or more and 80 parts by mass or less with respect to 100 parts by mass of the polymer component contained in the polymer composition.
  • N 2 SA nitrogen adsorption specific surface area
  • a 1 is a monovalent group bonded to L 1 with an imino group, an amide group, a (thio) carbonyl group, a (thio) carbonyloxy group, a sulfide or a polysulfide, or is protected.
  • a 2 is a monovalent group bonded to L 2 with an imino group, an amide group, a (thio) carbonyl group, a (thio) carbonyloxy group, a sulfide or a polysulfide, or is protected.
  • R 3 and R 4 each independently represent a hydrocarbyl group having 1 to 4 carbon atoms, n2 is 0 to 3, and m1 is 0 or 1.)
  • L 3 , R 3 , R 4 and n 2 are the same as in formula (2), and * indicates a site that binds to L 2.
  • a 3 are each independently, an imino group, an amido group, (thio) carbonyl group, a (thio) carbonyl group, secondary amino group, or a tertiary amino group
  • Z is a nitrogen atom
  • L 4 represents a single bond or a hydrocarbylene group having 1 to 20 carbon atoms
  • L 5 represents a hydrocarbylene group having 1 to 20 carbon atoms.
  • R 5 and R 6 each independently represent a hydrocarbyl group having 1 to 4 carbon atoms, n3 is 0 or 1, and t is 2 or 3).
  • R 7 and R 8 each independently represent a hydrocarbyl group having 1 to 20 carbon atoms
  • R 9 is a hydrocarbyl group having 1 to 20 carbon atoms, a hydrogen atom contained in the alkyl group, and -CH.
  • At least one of 2- is a substituted alkyl group having 1 to 20 carbon atoms substituted with a group containing at least one element selected from the group consisting of silicon, nitrogen, phosphorus, oxygen and sulfur, or nitrogen.
  • the polystyrene-equivalent weight average molecular weight of the conjugated diene polymer (A) measured by gel permeation chromatography can be 100,000 to 2,000,000.
  • a cross-linking agent can be contained.
  • One aspect of the crosslinked polymer according to the present invention is It is produced by using the polymer composition of any one of the above embodiments.
  • One aspect of the tire according to the present invention is It is the one using the crosslinked polymer of the said aspect.
  • the polymer composition according to the present invention it is possible to produce a crosslinked polymer (tire) having a highly balanced breaking strength and wear resistance.
  • (meth) acrylic acid- is a concept including both acrylic acid-and methacrylic acid-.
  • the polymer composition according to the present embodiment is (A) a polymer of a conjugated diene compound or a copolymer of a conjugated diene compound and an aromatic vinyl compound, and has an active polymerization terminal and the following general formula (1). ) To (4), a conjugated diene polymer, which is a reaction product with the compound represented by any of (4), and (B) nitrogen adsorption specific surface area (N 2 SA) of 75 m 2 / g or more and 130 m 2 / g or less. Contains carbon black and.
  • the polymer composition according to the present embodiment is an unvulcanized polymer composition obtained by kneading (A) conjugated diene-based polymer and (B) carbon black with other additives if necessary. It is a thing.
  • the polymer composition according to the present embodiment forms a crosslinked polymer by subjecting it to a crosslinking treatment such as vulcanization.
  • the polymer composition according to the present embodiment is (A) a polymer of a conjugated diene compound or a copolymer of a conjugated diene compound and an aromatic vinyl compound, and has an active polymerization terminal and the following.
  • a conjugated diene-based polymer which is a reaction product with a compound represented by any of the general formulas (1) to (4) (in the present specification, it is also simply referred to as "(A) conjugated diene-based polymer"). Contains.
  • a 1 is a monovalent group bonded to L 1 with an imino group, an amide group, a (thio) carbonyl group, a (thio) carbonyloxy group, a sulfide or a polysulfide, or is protected.
  • a 2 is a monovalent group bonded to L 2 with an imino group, an amide group, a (thio) carbonyl group, a (thio) carbonyloxy group, a sulfide or a polysulfide, or is protected.
  • a 3 are each independently, an imino group, an amido group, (thio) carbonyl group, a (thio) carbonyl group, secondary amino group, or a tertiary amino group
  • Z is a nitrogen atom
  • L 4 represents a single bond or a hydrocarbylene group having 1 to 20 carbon atoms
  • L 5 represents a hydrocarbylene group having 1 to 20 carbon atoms.
  • R 5 and R 6 each independently represent a hydrocarbyl group having 1 to 4 carbon atoms, n3 is 0 or 1, and t is 2 or 3).
  • R 7 and R 8 each independently represent a hydrocarbyl group having 1 to 20 carbon atoms
  • R 9 is a hydrocarbyl group having 1 to 20 carbon atoms, a hydrogen atom contained in the alkyl group, and -CH.
  • At least one of 2- is a substituted alkyl group having 1 to 20 carbon atoms substituted with a group containing at least one element selected from the group consisting of silicon, nitrogen, phosphorus, oxygen and sulfur, or nitrogen.
  • the conjugated diene-based polymer has a structural unit derived from the conjugated diene compound, and has a structure derived from any of the compounds of the above general formulas (1) to (4) at the active polymerization terminal.
  • a conjugated diene-based polymer first, a monomer containing a conjugated diene compound is polymerized to obtain a polymer having an active terminal (polymerization step), and then a polymer having an active terminal is obtained.
  • polymerization step a polymer having an active terminal
  • Examples of the conjugated diene compound that can be used in the polymerization include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, and 1,3-heptadiene. , 2-Phenyl-1,3-butadiene, 3-methyl-1,3-pentadiene, 2-chloro-1,3-butadiene and the like. Among these, 1,3-butadiene, isoprene and 2,3-dimethyl-1,3-butadiene are preferable.
  • the conjugated diene compound may be used alone or in combination of two or more.
  • the conjugated diene-based polymer (A) may be a homopolymer of the conjugated diene compound, but from the viewpoint of increasing the strength of the crosslinked polymer, it must be a copolymer of the conjugated diene compound and an aromatic vinyl compound. Is preferable. Above all, a copolymer containing 1,3-butadiene and styrene in a monomer composition is preferable in terms of high living property in anionic polymerization.
  • the (A) conjugated diene-based polymer is typically a conjugated diene compound and an aromatic vinyl compound. It may have a random copolymerized moiety having an irregular distribution of, and further have a block moiety composed of structural units derived from a conjugated diene compound or an aromatic vinyl compound.
  • aromatic vinyl compound examples include styrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, ⁇ -methylstyrene, 2,4-dimethylstyrene, 2,4-diisopropylstyrene, and the like.
  • the content of the aromatic vinyl compound is the low loss property of the obtained crosslinked polymer.
  • the content is preferably 3 to 55% by mass, preferably 5 to 50% by mass, based on 100% by mass of the total of the conjugated diene compound and the aromatic vinyl compound used for the polymerization. It is more preferable to do so.
  • the aromatic vinyl content of the conjugated diene polymer (A) can be measured by 1 1 H-NMR.
  • a monomer other than the conjugated diene compound and the aromatic vinyl compound may be used.
  • examples of other monomers include acrylonitrile, methyl (meth) acrylate, ethyl (meth) acrylate, hydroxyethyl (meth) acrylate and the like.
  • the amount of the other monomer used is preferably 25% by mass or less, more preferably 15% by mass or less, and preferably 10% by mass or less, based on 100% by mass of the total amount of the monomers used for the polymerization. Especially preferable.
  • any of a solution polymerization method, a gas phase polymerization method and a bulk polymerization method may be used, but the solution polymerization method is particularly preferable.
  • the polymerization type either a batch type or a continuous type may be used.
  • the solution polymerization method as an example of a specific polymerization method, a monomer containing a conjugated diene compound is polymerized in an organic solvent in the presence of a polymerization initiator and a randomizer used if necessary. The method can be mentioned.
  • an alkali metal compound or an alkaline earth metal compound can be used as the polymerization initiator.
  • alkyllithium such as methyllithium, ethyllithium, n-propyllithium, n-butyllithium, sec-butyllithium and tert-butyllithium, 1,4-dilithiobtan, phenyllithium and stillbenlithium.
  • the total amount of the polymerization initiator used is preferably 0.2 to 20 mmol with respect to 100 g of the monomer used for the polymerization.
  • the polymerization initiator may be used alone or in combination of two or more.
  • the polymerization reaction is carried out in the presence of a compound obtained by mixing an alkali metal compound or an alkaline earth metal compound with a compound having a functional group that interacts with silica (hereinafter, also referred to as "modification initiator"). You may go with.
  • modification initiator a functional group that interacts with silica can be introduced into the polymerization initiation terminal of the (A) conjugated diene-based polymer.
  • “interaction” means an intermolecular force which forms a covalent bond between molecules or is weaker than a covalent bond (for example, ion-dipole interaction, dipole-dipole interaction, etc.
  • the "functional group that interacts with silica” preferably has at least one selected from the group consisting of nitrogen atoms, sulfur atoms, phosphorus atoms and oxygen atoms.
  • the modification initiator is preferably a reaction product of a lithium compound such as alkyllithium and a nitrogen-containing compound such as a secondary amine compound.
  • a nitrogen-containing compound such as a secondary amine compound.
  • nitrogen-containing compound include, for example, dimethylamine, diethylamine, dipropylamine, dibutylamine, dodecamethyleneimine, N, N'-dimethyl-N'-trimethylsilyl-1,6-diaminohexane, piperidine, pyrrolidine, and the like.
  • a modification initiator is prepared by previously mixing an alkali metal compound or an alkaline earth metal compound with a compound having a functional group that interacts with silica. The prepared modification initiator may be added to the polymerization system to carry out the polymerization.
  • an alkali metal compound or alkaline earth metal compound and a compound having a functional group that interacts with silica are added to the polymerization system, and both are mixed in the polymerization system to prepare a modification initiator.
  • Polymerization may be carried out.
  • a nitrogen-containing alkyllithium compound can also be used.
  • a reaction product of 3-dimethylaminopropyllithium and isoprene can be used.
  • the randomizer can be used for the purpose of adjusting the vinyl bond content, which represents the content of vinyl bonds (1,2-bonds and 3,4-bonds) in the polymer.
  • randomizers include dimethoxybenzene, tetrahydrofuran, dimethoxyethane, diethylene glycol dibutyl ether, diethylene glycol dimethyl ether, 2,2-di (tetrahydrofuryl) propane, 2- (2-ethoxyethoxy) -2-methylpropane, triethylamine, pyridine. , N-Methylmorpholine, tetramethylethylenediamine and the like. These can be used alone or in combination of two or more.
  • the organic solvent used for the polymerization may be any organic solvent that is inert to the reaction, and for example, aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons and the like can be used. Of these, hydrocarbons having 3 to 8 carbon atoms are preferable, and specific examples thereof include propane, n-butene, isobutane, n-pentane, isopentane, n-hexane, cyclohexane, propene, 1-butene, isobutene, and 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-Pentyne, cyclohexene and the like can be mentioned.
  • the organic solvent one type can be used alone or two or more types can be used in combination.
  • the monomer concentration in the reaction solvent is preferably 5 to 50% by mass, preferably 10 to 30% by mass, from the viewpoint of maintaining a balance between productivity and ease of polymerization control. More preferred.
  • the temperature of the polymerization reaction is preferably ⁇ 20 ° C. to 150 ° C., more preferably 0 ° C. to 120 ° C., and particularly preferably 20 ° C. to 100 ° C. Further, it is preferable that the polymerization reaction is carried out under a pressure sufficient to keep the monomer substantially in the liquid phase. Such pressure can be obtained by a method such as pressurizing the inside of the reactor with a gas that is inert to the polymerization reaction. By such a polymerization reaction, a conjugated diene-based polymer having an active terminal can be obtained.
  • the vinyl bond content in the structural unit derived from the conjugated diene compound is preferably 30 to 65 mol%, more preferably 33 to 62 mol%, and 35 to 35 to It is particularly preferably 60 mol%. If the vinyl bond content is less than 30 mol%, the grip characteristics tend to be too low, and if it exceeds 65 mol%, the wear resistance of the obtained crosslinked polymer tends to be deteriorated.
  • the "vinyl bond content” is a value indicating the content ratio of the structural unit having a vinyl bond to all the structural units derived from the conjugated diene compound in the conjugated diene polymer, and is 1 H-. It is a value measured by NMR.
  • a 1 is a monovalent group bonded to L 1 with an imino group, an amide group, a (thio) carbonyl group, a (thio) carbonyloxy group, a sulfide or a polysulfide, or is protected.
  • the hydrocarbylene group having 1 to 20 carbon atoms of L 1 includes a linear or branched alkanediyl group having 1 to 20 carbon atoms and a cycloalkylene group having 3 to 20 carbon atoms. Examples thereof include an arylene group having 6 to 20 carbon atoms.
  • a linear or branched alkyl group having 1 to 4 carbon atoms and a cycloalkyl group having 3 to 4 carbon atoms are used as the hydrocarbyl group having 1 to 4 carbon atoms of R 1 and R 2, a linear or branched alkyl group having 1 to 4 carbon atoms and a cycloalkyl group having 3 to 4 carbon atoms are used. Can be mentioned.
  • the (thio) carbonyl group represents a carbonyl group and a thiocarbonyl group
  • the (thio) carbonyloxy group represents a carbonyloxy group and a thiocarbonyloxy group
  • the (thio) epoxy group represents an epoxy group and a thioepoxy group.
  • the (thio) isocyanate group represents an isocyanate group and a thioisocyanate group
  • the (thio) formyl group represents a formyl group and a thioformyl group
  • the (thio) carboxylic acid ester represents a carboxylic acid ester and a thiocarboxylic acid ester.
  • Specific examples of the compound represented by the above general formula (1) include N, N-dimethylaminopropyltriethoxysilane, N, N-bis (trimethylsilyl) aminopropylmethyldiethoxysilane, and N-benzylidene-3-tri. Examples thereof include ethoxysilyl-1-propaneamine, N- (3-trimethoxysilylpropyl) -4,5-dihydroimidazole, N- (3-triethoxysilylpropyl) -4,5-dihydroimidazole and the like.
  • a 2 is a monovalent group bonded to L 2 with an imino group, an amide group, a (thio) carbonyl group, a (thio) carbonyloxy group, a sulfide or a polysulfide, or is protected.
  • the hydrocarbylene group having 1 to 20 carbon atoms of L 2 and L 3 is a linear or branched alkanediyl group having 1 to 20 carbon atoms and a cyclo having 3 to 20 carbon atoms. Examples thereof include an alkylene group and an arylene group having 6 to 20 carbon atoms.
  • the hydrocarbyl group having 1 to 4 carbon atoms of R 3 and R 4 a linear or branched alkyl group having 1 to 4 carbon atoms and a cycloalkyl group having 3 to 4 carbon atoms are used. Can be mentioned.
  • Specific examples of the compound represented by the above general formula (2) include N, N-bis (trimethoxysilylpropyl) aminopropyl-3-imidazole and N, N-bis (triethoxysilylpropyl) aminopropyl-1.
  • -Imidazole N, N-bis (trimethoxysilyl) aminopropylmethyldiethylsilane, N, N, N-tris (triethoxysilylpropyl) amine, N, N, N', N'-tetrakis (3-triethoxy) Cyrilpropyl) -1,3-diaminopropane and the like can be mentioned.
  • a 3 are each independently, an imino group, an amido group, (thio) carbonyl group, a (thio) carbonyl group, secondary amino group, or a tertiary amino group
  • Z is a nitrogen atom
  • L 4 represents a single bond or a hydrocarbylene group having 1 to 20 carbon atoms
  • L 5 represents a hydrocarbylene group having 1 to 20 carbon atoms.
  • R 5 and R 6 each independently represent a hydrocarbyl group having 1 to 4 carbon atoms, n3 is 0 or 1, and t is 2 or 3).
  • Z is a divalent or trivalent group having 1 to 20 carbon atoms which may contain a nitrogen atom, but preferably contains a nitrogen atom.
  • hydrocarbylene group of 1 to 20 carbon atoms hydrocarbylene group and L 5 of the L 4 having 1 to 20 carbon atoms, having 1 to 20 carbon atoms, straight or branched Examples thereof include an alkanediyl group, a cycloalkylene group having 3 to 20 carbon atoms, and an arylene group having 6 to 20 carbon atoms.
  • Specific examples of the compound represented by the general formula (3) include compounds represented by the following formulas (M-1) to (M-4).
  • R 11 represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms
  • n5 represents an integer of 1 to 10.
  • R 7 and R 8 each independently represent a hydrocarbyl group having 1 to 20 carbon atoms
  • R 9 is a hydrocarbyl group having 1 to 20 carbon atoms, a hydrogen atom contained in the alkyl group, and -CH.
  • At least one of 2- is a substituted alkyl group having 1 to 20 carbon atoms substituted with a group containing at least one element selected from the group consisting of silicon, nitrogen, phosphorus, oxygen and sulfur, or nitrogen.
  • the hydrocarbyl groups having 1 to 20 carbon atoms of R 7 and R 8 include linear or branched alkyl groups having 1 to 20 carbon atoms and cycloalkyl groups having 3 to 20 carbon atoms. Examples thereof include an aryl group having 6 to 20 carbon atoms.
  • Specific examples of the compound represented by the above general formula (4) include N-phenyl-2,2-dimethoxy-1-aza-2-silacyclopentane, N- (3-triethoxysilylpropyl) -2, Examples thereof include 2-dimethoxy-1-aza-2-silacyclopentane.
  • the specific modifier may be used alone, but the specific modifier and the modifier other than the specific modifier (hereinafter, "other modifiers"" Also called.) May be used.
  • the other denaturing agent is not particularly limited as long as it is a compound having a functional group that interacts with the filler and capable of reacting with the active terminal of the polymer.
  • the above denaturation reaction can be carried out as, for example, a solution reaction.
  • This solution reaction may be carried out using a solution containing an unreacted monomer after the completion of the polymerization reaction, and the conjugated diene polymer contained in the solution is isolated and dissolved in an appropriate solvent such as cyclohexane. You may go.
  • the modification reaction may be carried out by either a batch type or a continuous type.
  • the method of adding the denaturant is not particularly limited, and examples thereof include a method of adding the denaturant all at once, a method of adding the denaturant in divided portions, and a method of continuously adding the denaturant.
  • the ratio of the specific modifier (the total amount when two or more kinds are used) is preferably 0.2 mol or more with respect to 1 mol of the metal atom involved in the polymerization reaction of the polymerization initiator. More preferably, it is 0.4 mol or more.
  • the amount is 0.2 mol or more, the modification reaction of the polymer terminal by the specific modifier can be sufficiently proceeded, and the interaction with the filler at the terminal modification site can be sufficiently strengthened.
  • the upper limit of the usage ratio of the specific denaturant is 1.5 with respect to 1 mol of the metal atom involved in the polymerization reaction of the polymerization initiator.
  • the amount is preferably less than 1.2 mol, more preferably less than 1.2 mol.
  • the ratio of the other denaturants used is specified from the viewpoint of sufficiently advancing the reaction between the conjugated diene polymer and the specific denaturant. It is preferably 30 mol% or less, more preferably 20 mol% or less, and particularly preferably 10 mol% or less, based on the total usage ratio of the denaturant and other denaturants.
  • 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 ° C. to 120 ° C., and preferably 20 ° C. to 100 ° C. Especially preferable.
  • the reaction time of the degeneration reaction is preferably 1 minute to 5 hours, more preferably 2 minutes to 1 hour.
  • the (A) conjugated diene polymer contained in the reaction solution can be isolated by a known desolvation method such as steam stripping and a drying operation such as heat treatment.
  • the Mooney viscosity of the obtained (A) conjugated diene polymer may be adjusted by adding a stretching oil or the like, if necessary. By this treatment, workability can be improved.
  • the spreading oil include aroma oil, naphthenic oil, paraffin oil and the like.
  • the blending amount of the spreading oil may be appropriately set according to the monomer used for the polymerization and the like, and is, for example, 10 to 50 parts by mass with respect to 100 parts by mass of the conjugated diene polymer.
  • the (A) conjugated diene-based polymer can be obtained.
  • the compatibility with the filler can be improved, and a polymer composition having improved processability can be obtained.
  • a polymer composition containing such a conjugated diene-based polymer (A) heat generation, breaking strength, abrasion resistance, fuel efficiency, wet grip, etc. required for applications such as automobile tires can be obtained. It is possible to obtain a tire (crosslinked polymer) which is excellent but has low rolling resistance.
  • the conjugated diene polymer (A) preferably has a structure derived from any of the compounds of the above general formulas (1) to (4) at at least one end of the polymer.
  • the conjugated diene polymer (A) has such a structure, the dispersibility of a filler such as carbon black or silica is further improved when applied to, for example, tire applications, and in terms of low loss resistance and wear resistance. , It is preferable in that it produces a higher improvement effect.
  • the polystyrene-equivalent weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) of the conjugated diene polymer is preferably 100,000 to 2,000,000.
  • Mw is smaller than 100,000, the crosslinked polymer of the polymer composition according to the present embodiment tends to have low loss resistance and wear resistance, and when it is larger than 2,000,000, it tends to be deteriorated.
  • the processability of the polymer composition tends to decrease.
  • the weight average molecular weight (Mw) of the obtained conjugated diene polymer (A) is more preferably 150,000 to 1,500,000, still more preferably 200,000 to 1,000,000.
  • the molecular weight distribution of the conjugated diene polymer that is, the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is preferably 1.5 to 3.0, more preferably. Is 1.5 to 2.5, and particularly preferably 1.5 to 2.2.
  • Mw / Mn the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn)
  • the polymer composition according to the present embodiment has (B) a carbon black having a nitrogen adsorption specific surface area (N 2 SA) of 75 m 2 / g or more and 130 m 2 / g or less (in the present specification, simply " (B) Also referred to as "carbon black”).
  • the polymer composition according to the present embodiment contains (B) carbon black having a specific nitrogen adsorption specific surface area, so that the (A) conjugated diene-based copolymer and (B) carbon black are compatible with each other. Therefore, it is possible to obtain a polymer composition having improved processability.
  • the inclusion of (B) carbon black provides an excellent reinforcing effect, and is highly balanced in breaking strength, wear resistance and fuel efficiency. A crosslinked polymer (tire) can be produced.
  • the nitrogen adsorption specific surface area (N 2 SA) of carbon black is 75 m 2 / g or more, preferably 78 m 2 / g or more, more preferably 82 m 2 / g or more, and particularly preferably 85 m. It is 2 / g or more. If N 2 SA is less than 75 m 2 / g, a sufficient reinforcing effect cannot be obtained, and a crosslinked polymer having excellent breaking strength and wear resistance may not be obtained.
  • the N 2 SA is 130 m 2 / g or less, preferably 125 m 2 / g or less, more preferably 123 m 2 / g or less, and particularly preferably 120 m 2 / g or less. When N 2 SA exceeds 130 m 2 / g, fuel efficiency tends to deteriorate.
  • carbon black N 2 SA can be measured according to the method described in JIS K6217-2: 2001.
  • the content ratio of (B) carbon black is 30 parts by mass or more, preferably 35 parts by mass or more, and more preferably 40 parts by mass with respect to 100 parts by mass of the polymer component contained in the polymer composition. That is all.
  • the content ratio of (B) carbon black is 80 parts by mass or less, preferably 75 parts by mass or less, with respect to 100 parts by mass of the polymer component contained in the polymer composition.
  • the content ratio of carbon black exceeds 80 parts by mass, the fuel efficiency of the obtained crosslinked polymer (tire) tends to deteriorate.
  • the content ratio of (B) carbon black is within the above range, a crosslinked polymer (tire) having a highly balanced balance in breaking strength, wear resistance and fuel efficiency can be produced.
  • the polymer composition according to the present embodiment may contain other diene-based polymers other than (A) conjugated diene-based polymer and (B) carbon black, if necessary.
  • Fillers silane coupling agents, cross-linking agents, acidic compounds, spreading oils (process oils), antioxidants, vulcanization accelerators, as well as vulcanization aids, processing aids, scorch inhibitors and zinc oxide as needed.
  • Softeners colorants, flame retardants, lubricants, foaming agents, plasticizers, antioxidants, UV inhibitors, antistatic agents, color inhibitors, etc., depending on the purpose of use of the polymer composition. Can be used.
  • the polymer composition according to the present embodiment may contain other diene-based polymers other than the (A) conjugated diene-based polymer.
  • a diene-based polymer is not particularly limited as long as it has a repeating unit derived from a conjugated diene compound, and for example, natural rubber, polybutadiene, polyisoprene, ethylene-propylene-diene rubber, styrene-butadiene rubber, acrylonitrile-. Examples include butadiene rubber.
  • the content ratio of the other polymers is when the total amount of the polymer components contained in the polymer composition is 100 parts by mass. It is preferably 50 parts by mass or less, more preferably 40 parts by mass or less, and particularly preferably 35 parts by mass or less.
  • the polymer composition according to the present embodiment may contain a filler other than (B) carbon black in order to further improve the low loss property, abrasion resistance and wet grip property of the obtained crosslinked polymer.
  • a filler include mica such as silica, calcium carbonate and sericite, aluminum hydroxide, magnesium oxide, magnesium hydroxide, clay, talc, alumina, titanium oxide and mica. These fillers may be used alone or in combination of two or more. Among these fillers, silica is particularly preferable.
  • silica examples include wet silica (hydrous silicic acid), dry silica (silicic anhydride), calcium silicate, and aluminum silicate. Among these, wet silica is preferable because it has a large number of silanol groups.
  • the nitrogen adsorption specific surface area (N 2 SA) of silica is preferably 40 m 2 / g or more, more preferably 50 m 2 / g or more, still more preferably 100 m 2 / g or more, and particularly preferably 150 m. It is 2 / g or more.
  • the N 2 SA of silica is preferably 300 m 2 / g or less, more preferably 250 m 2 / g or less, and particularly preferably 20 m 2 / g or less. When the N 2 SA of silica is within the above range, the dispersibility of silica in the polymer composition is improved, so that the workability is improved, and the breaking strength, fuel efficiency and steering stability are highly balanced. In some cases, an excellent crosslinked polymer (tire) can be produced.
  • the N 2 SA of silica is a value measured by the BET method according to the method described in ASTM D3037-81.
  • the content ratio of silica is preferably 10 parts by mass or more with respect to 100 parts by mass of the polymer component contained in the polymer composition. It is preferably 20 parts by mass or more, and particularly preferably 25 parts by mass or more.
  • the silica content is preferably 100 parts by mass or less, more preferably 80 parts by mass or less, and even more preferably 70 parts by mass with respect to 100 parts by mass of the polymer component contained in the polymer composition. It is not more than parts by mass, and particularly preferably 60 parts by mass or less.
  • the content ratio of silica is within the above range, the dispersibility of silica in the polymer composition is improved, so that the processability is improved, and the breaking strength, fuel efficiency and steering stability are highly balanced. In some cases, a crosslinked polymer (tire) can be produced.
  • silane coupling agent examples include bis (3-triethoxysilylpropyl) tetrasulfide, bis (3-triethoxysilylpropyl) trisulfide, bis (3-triethoxysilylpropyl) disulfide, and bis (2-triethoxy).
  • Cyrilethyl) tetrasulfide bis (3-trimethoxysilylpropyl) tetrasulfide, bis (2-trimethoxysilylethyl) tetrasulfide, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 2-mercaptoethyl Trimethoxysilane, 2-mercaptoethyltriethoxysilane; 3-trimethoxysilylpropyl-N, N-dimethylthiocarbamoyltetrasulfide, 3-triethoxysilylpropyl-N, N-dimethylthiocarbamoyltetrasulfide, 2-triethoxy Cyrilethyl-N, N-dimethylthiocarbamoyltetrasulfide, 3-trimethoxysilylpropylbenzothiazolyltetrasulfide, 3-trie
  • the ratio of the silane coupling agent used is preferably 0.5 to 20 parts by mass with respect to 100 parts by mass of the filler component.
  • the ratio of the silane coupling agent used is within the above range, sufficient reinforcing properties and fracture resistance can be imparted to the crosslinked polymer formed from the polymer composition, and the abrasion resistance of the crosslinked polymer is improved. You may be able to do it.
  • Cross-linking agent examples include sulfur, sulfur halides, organic peroxides, quinonedioximes, organic polyvalent amine compounds, alkylphenol resins having a methylol group, and the like. Of these, sulfur is usually used as the cross-linking agent.
  • the ratio of the cross-linking agent used is preferably 0.1 to 10 parts by mass, and more preferably 0.5 to 5 parts by mass with respect to 100 parts by mass of the polymer component.
  • saturated fatty acids having 12 to 24 carbon atoms and metal salts thereof are preferably used.
  • Specific examples of acidic compounds include lauric acid, tridecylic acid, myristic acid, pentadecylic acid, palmitic acid, margaric acid, stearic acid, nonadecylic acid, arachidic acid, henicosylic acid, bechenic acid, tricosylic acid, lignoceric acid, and these.
  • saturated fatty acids include calcium salt and zinc salt. These acidic compounds can be used alone or in combination of two or more. Of these, stearic acid is preferred.
  • the ratio of the acidic compound used is preferably 0.3 to 15 parts by mass with respect to 100 parts by mass of the polymer component.
  • the spreading oil include aroma oil, naphthenic oil, paraffin oil and the like.
  • the proportion of the spreading oil used is 0 to 50 parts by mass with respect to 100 parts by mass of the polymer component.
  • antiaging agent examples include N- (1,3-dimethylbutyl) -N'-phenyl-p-phenylenediamine, N-phenyl-N'-isopropyl-p-phenylenediamine and the like.
  • the ratio of the anti-aging agent used is 0.5 to 5 parts by mass with respect to 100 parts by mass of the polymer component.
  • vulcanization aid examples include zinc oxide and the like.
  • the ratio of the vulcanization aid used is 1 to 5 parts by mass with respect to 100 parts by mass of the polymer component.
  • vulcanization accelerator examples include guadinin-based, aldehyde-amine-based, aldehyde-ammonia-based, thiazole-based, sulfenamide-based, thiourea-based, thiuram-based, dithiocarbamate-based, and zantate-based compounds.
  • Preferred specific examples of the vulcanization accelerator are sulfenamides such as N-cyclohexyl-2-benzothiazyl sulfenamide (CBS) and N-tetra-butyl-2-benzothiazyl sulfenamide (TBBS).
  • CBS N-cyclohexyl-2-benzothiazyl sulfenamide
  • TBBS N-tetra-butyl-2-benzothiazyl sulfenamide
  • vulcanization accelerators examples include vulcanization accelerators.
  • the proportion of the vulcanization accelerator used is appropriately determined in consideration of the type and
  • the polymer composition according to the present embodiment can be prepared by kneading each of the above components using, for example, a kneader such as a plastomill, a Banbury mixer, a roll, or an internal mixer. it can. For example, it is preferable to prepare by the following method.
  • first-stage kneading it is preferable to knead the (A) conjugated diene polymer and (B) carbon black together with other fillers and silane coupling agents added as needed. Further, in the first-stage kneading, other polymers, a spreading oil, an antiaging agent and the like are also kneaded together, if necessary. Further, in the first-stage kneading, the acidic compounds, which are preferably kneaded in the second-stage kneading, may be kneaded together.
  • the filler By applying the filler to the first-stage kneading, the dispersibility of these is likely to be improved, and the fuel efficiency performance of the tire (crosslinked polymer) formed from the obtained polymer composition may be improved.
  • a silane coupling agent When a silane coupling agent is used for the first-stage kneading, first, (A) conjugated diene polymer, (B) carbon black, other polymer, and if necessary, other fillers are kneaded. After that, it is preferable to add (post-add) a silane coupling agent and further knead.
  • the obtained polymer composition becomes more processable, and the crosslinked polymer formed from the polymer composition has more excellent low hysteresis. It will have characteristics. Further, when the polymer composition contains silica as a filler, the dispersibility of silica can be improved.
  • the timing of adding the silane coupling agent depends on the type of silica, the ratio of silica used, the kneading conditions, etc., and the use of (A) conjugated diene polymer and other polymers. It is determined as appropriate in consideration of the ratio.
  • (A) conjugated diene polymer (B) carbon black and other polymers are blended and kneaded for 0.5 to 10 minutes, and then the silane cup is used. It is preferable to add a ring agent and knead for 0.5 to 10 minutes.
  • the kneading machine used for the first-stage kneading examples include an open type or a closed type kneader such as a plast mill, a Banbury mixer, a roll, and an internal mixer. Further, in the first-stage kneading, the kneading temperature is set to 30 ° C. to 180 ° C., preferably 50 ° C. to 160 ° C.
  • the method is not limited to the method of adding the silane coupling agent afterwards and kneading, and the silane coupling agent is used for the first-stage kneading.
  • a kneaded product containing a silane coupling agent may be obtained by a method of kneading all the components at once.
  • a method of adding other polymers and additives after preparing a masterbatch in which (A) conjugated diene polymer, (B) carbon black, silica as a filler and a silane coupling agent are kneaded may be used. ..
  • the second-stage kneading is a step of adding at least a cross-linking agent to the kneaded product obtained in the first-stage kneading and kneading the kneaded product and the cross-linking agent to obtain a polymer composition.
  • the acidic compound is kneaded together with the kneaded product obtained in the first-stage kneading and the cross-linking agent.
  • zinc oxide and the vulcanization accelerator are also kneaded together, if necessary.
  • a polymer composition can be obtained by a method of simultaneously kneading an acidic compound and other components such as zinc oxide and a vulcanization accelerator.
  • the obtained polymer composition has more excellent processability, and the crosslinked polymer formed from the polymer composition has more excellent low loss property. Will have.
  • the kneading machine used in the first stage kneading is used. Further, in the second stage kneading, the kneading temperature is set to 30 ° C. to 130 ° C., preferably 50 ° C. to 110 ° C.
  • the polymer composition obtained by the above-mentioned production method is an unvulcanized rubber composition, and a crosslinked polymer is formed by performing a crosslinking treatment such as vulcanization, for example.
  • the crosslinked polymer formed from the polymer composition according to this embodiment is suitably used as a tire, specifically, a tread of a tire.
  • the tire formed from the polymer composition according to the present embodiment has high strength in the tread and a desired shape in the tread, so that excellent performance can be obtained.
  • the crosslinked polymer formed from the polymer composition according to the present embodiment can also be used as a tire member other than a tread, a vibration-proof rubber, a fender, a belt, a hose, and other industrial products.
  • N 2 SA nitrogen adsorption specific surface area
  • a plast mill (content capacity 250 cc) with a temperature control device, as the first stage kneading, under the conditions of a filling rate of 72% and a rotation speed of 60 rpm, the polymer components shown in Table 2 or Table 3 below, carbon black, A silane coupling agent, stearic acid, an antiaging agent, and zinc oxide were kneaded.
  • the second-stage kneading the kneaded product obtained above is cooled to room temperature, and then sulfur and a vulcanization accelerator are kneaded to form the polymers of Examples 1 to 13 and Comparative Examples 1 to 10. I got something.
  • each of the obtained polymer compositions was molded and vulcanized at 160 ° C. for a predetermined time with a vulcanization press to obtain each crosslinked polymer having a predetermined shape to be subjected to the following evaluation test.
  • Table 1 shows the physical property values of each polymer synthesized above.
  • Tables 2 and 3 below show the composition and evaluation results of each polymer composition.
  • the present invention is not limited to the above embodiment, and various modifications are possible.
  • the present invention includes substantially the same configurations as those described in the embodiments (eg, configurations with the same function, method and result, or configurations with the same purpose and effect).
  • the present invention also includes a configuration in which a non-essential part of the configuration described in the above embodiment is replaced with another configuration.
  • the present invention also includes a configuration that exhibits the same effects as the configuration described in the above embodiment or a configuration that can achieve the same object.
  • the present invention also includes a configuration in which a known technique is added to the configuration described in the above embodiment.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Tires In General (AREA)

Abstract

La présente invention concerne une composition polymère qui a une bonne aptitude au traitement et est appropriée pour la production d'un pneumatique qui a un bon équilibre entre la résistance à la rupture et la résistance à l'usure.　Une composition polymère selon la présente invention contient : (A) un polymère diène conjugué qui est un polymère d'un composé diène conjugué ou un copolymère d'un composé diène conjugué et d'un composé vinylique aromatique et qui est un produit de réaction d'une extrémité de polymérisation active et d'un composé représenté par l'une des formules générales (1) à (4) ; et (B) un noir de carbone ayant une surface spécifique d'adsorption d'azote (N2SA) de 75 m2/g à 130 m2/g. Cette composition polymère contient de 30 parties en masse à 80 parties en masse du noir de carbone (B) par rapport à 100 parties en masse du composant polymère contenu dans cette composition polymère.
PCT/JP2020/027997 2019-07-26 2020-07-20 Composition polymère, polymère réticulé et pneumatique WO2021020189A1 (fr)

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WO2022195978A1 (fr) * 2021-03-19 2022-09-22 株式会社ブリヂストン Composition de caoutchouc et pneumatique
WO2022195977A1 (fr) * 2021-03-19 2022-09-22 株式会社ブリヂストン Composition de caoutchouc et pneumatique
JP7188519B1 (ja) 2021-09-07 2022-12-13 横浜ゴム株式会社 タイヤ用ゴム組成物

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JP2007077317A (ja) * 2005-09-15 2007-03-29 Bridgestone Corp ゴム組成物およびそれを用いたタイヤ
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WO2022195978A1 (fr) * 2021-03-19 2022-09-22 株式会社ブリヂストン Composition de caoutchouc et pneumatique
WO2022195977A1 (fr) * 2021-03-19 2022-09-22 株式会社ブリヂストン Composition de caoutchouc et pneumatique
JP7188519B1 (ja) 2021-09-07 2022-12-13 横浜ゴム株式会社 タイヤ用ゴム組成物
JP2023038668A (ja) * 2021-09-07 2023-03-17 横浜ゴム株式会社 タイヤ用ゴム組成物

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