WO2010061802A1 - Procédé de fabrication d’un polymère diène conjugué modifié, polymère diène conjugué modifié, composition de caoutchouc et pneu - Google Patents

Procédé de fabrication d’un polymère diène conjugué modifié, polymère diène conjugué modifié, composition de caoutchouc et pneu Download PDF

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WO2010061802A1
WO2010061802A1 PCT/JP2009/069746 JP2009069746W WO2010061802A1 WO 2010061802 A1 WO2010061802 A1 WO 2010061802A1 JP 2009069746 W JP2009069746 W JP 2009069746W WO 2010061802 A1 WO2010061802 A1 WO 2010061802A1
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conjugated diene
diene polymer
component
modified conjugated
group
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Japanese (ja)
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了司 田中
卓男 曽根
耕一郎 谷
孝博 中村
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JSR Corp
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JSR Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
    • C08C19/00—Chemical modification of rubber
    • C08C19/30—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule
    • C08C19/42—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule reacting with metals or metal-containing groups
    • C08C19/44—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule reacting with metals or metal-containing groups of polymers containing metal atoms exclusively at one or both ends of the skeleton
    • 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
    • B60C1/0016—Compositions of the tread
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
    • C08C19/00—Chemical modification of rubber
    • C08C19/25—Incorporating silicon atoms into the molecule
    • 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
    • C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
    • C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers

Definitions

  • the present invention relates to a method for producing a modified conjugated diene polymer, a modified conjugated diene polymer, a rubber composition, and a tire. More specifically, the present invention relates to low exothermic property, low temperature characteristics, and wear resistance without impairing workability. The present invention relates to a method for producing a modified conjugated diene polymer capable of producing an excellent rubber product, a modified conjugated diene polymer produced by this production method, a rubber composition, and a tire.
  • silica is included as a filler.
  • the interaction between the rubber composition and silica is usually weak, there is a problem that a large amount of filler must be used in order to produce a material having desired properties.
  • a functional group that interacts with a filler is used for the polymerization active terminal of a conjugated diene polymer obtained by anionic polymerization of a conjugated diene compound using an organolithium compound as a polymerization initiator.
  • a rubber composition containing a modified conjugated diene polymer modified with an alkoxysilane derivative has been proposed.
  • a rubber composition containing a modified conjugated diene polymer having a cis 1,4-polybutadiene structure which is particularly important for tire sidewall rubber and tread rubber.
  • the modification effect in the rubber composition containing silica is not always sufficient.
  • a rubber composition containing a modified conjugated diene polymer having a cis 1,4-polybutadiene structure has almost no modification effect by adding silica.
  • the present invention has been made in view of such problems of the prior art, and the object of the present invention is excellent in low heat generation, low temperature characteristics, wear resistance, etc. without impairing workability.
  • Another object of the present invention is to provide a method for producing a modified conjugated diene polymer capable of producing a rubber product.
  • the problem is to provide a modified conjugated diene polymer capable of producing a rubber product excellent in low heat build-up, low temperature characteristics, wear resistance and the like without impairing processability.
  • the subject is to provide a rubber composition capable of producing a rubber product excellent in low heat build-up, low temperature characteristics, abrasion resistance, etc. without impairing processability.
  • the present inventors have obtained a process for obtaining a high molecular weight component (A) having a predetermined property in a method for producing a modified conjugated diene polymer, and a low property having a predetermined property. Achieving the above-mentioned problems by employing a production method comprising a step of obtaining a molecular weight component (B) and a step of condensing an alkoxysilyl group after mixing the components (A) and (B). As a result, the present invention has been completed.
  • the present inventors have found that the above problem can be achieved by obtaining a modified conjugated diene polymer by the method for producing a modified conjugated diene polymer of the present invention, and have completed the present invention.
  • modified conjugated diene polymer production method modified conjugated diene polymer, rubber composition, and tire are provided.
  • the vinyl content is less than 10%, the cis 1,4-bond content is 75% or more, and the polystyrene equivalent weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) is 250,000 to 800,000.
  • An active terminal having a content of less than 10%, a cis 1,4-bond content of 75% or more, and a weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography (GPC) of 10,000 to 150,000.
  • a second alkoxysilyl group is introduced into the active terminal of the second conjugated diene polymer having a second alkoxysilane compound, and the component (B)
  • a modified conjugated diene polymer comprising: a step of obtaining and condensing the first alkoxysilyl group and the second alkoxysilyl group after mixing the component (A) and the component (B) Manufacturing method.
  • (C) component a rare earth element-containing compound corresponding to atomic numbers 57 to 71 in the periodic table, or a reaction product of the rare earth element-containing compound and a Lewis base (d) component; alumoxane and general formula (1): AlR 1 R 2 Organoaluminum compound corresponding to at least one of the compounds represented by R 3 (In the general formula (1), R 1 and R 2 are each independently a hydrocarbon group having 1 to 10 carbon atoms or a hydrogen atom. R 3 represents a hydrocarbon group having 1 to 10 carbon atoms, provided that R 3 may be the same as or different from R 1 or R 2 .
  • a modified conjugated diene polymer capable of producing a rubber product excellent in low exothermic property, low temperature characteristics, wear resistance, etc. without impairing processability. There is an effect that can be manufactured.
  • the modified conjugated diene polymer of the present invention has an effect that it is possible to produce a rubber product excellent in low exothermic property, low temperature characteristic, wear resistance and the like without impairing processability.
  • the rubber composition of the present invention has an effect that it is possible to produce a rubber product excellent in low heat generation, low temperature characteristics, wear resistance, etc. without impairing processability.
  • conjugated diene polymer indicates both the first and second conjugated diene polymers, and when it is described as “modifier”, When both the first and second alkoxysilyl compounds are shown and “alkoxysilyl group” is described, both the first and second alkoxysilyl groups are shown.
  • the method for producing a modified conjugated diene polymer of the present invention comprises a step of obtaining a high molecular weight component (A) having a predetermined property, a step of obtaining a low molecular weight component (B) having a predetermined property, and (A ) Component and (B) component are mixed, and then the method includes a step of condensing the first alkoxysilyl group and the second alkoxysilyl group.
  • the component (A) is obtained by introducing a first alkoxysilyl group (hereinafter also referred to as “modification reaction”) to the active terminal of the first conjugated diene polymer using the first alkoxysilane compound. It is an ingredient.
  • modification reaction a first alkoxysilyl group
  • the component (A) preferably has a structural unit derived from at least one conjugated diene compound selected from the group consisting of 1,3-butadiene, isoprene, and 2,3-dimethyl-1,3-butadiene.
  • the first conjugated diene polymer has a vinyl content of less than 10%, a cis 1,4-bond content of 75% or more, and a weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography (GPC) ( (Hereinafter referred to as “Mw”) is a polymer of a conjugated diene compound having 250,000 to 800,000 and having an active end.
  • the vinyl content of the first conjugated diene polymer is less than 10%, preferably less than 5%, and more preferably less than 2%. If the vinyl content is 10% or more, mechanical properties such as wear resistance of the rubber product after vulcanization may be inferior.
  • the vinyl content can be easily adjusted by controlling the temperature of the polymerization reaction.
  • the cis 1,4-bond content of the first conjugated diene polymer is 75% or more, preferably 85% or more, and more preferably 90 to 99.9%.
  • the cis 1,4-bond content can be easily adjusted by controlling the temperature of the polymerization reaction.
  • the Mw of the first conjugated diene polymer is 250,000 to 800,000, preferably 270,000 to 700,000, and more preferably 300,000 to 600,000. If the Mw is less than 250,000, mechanical properties such as wear resistance of the rubber product after vulcanization may be inferior. On the other hand, if it exceeds 800,000, workability may be inferior. In addition, Mw can be adjusted by controlling the usage-amount of the catalyst used for a polymerization reaction.
  • the component (B) is obtained by introducing a second alkoxysilyl group (hereinafter also referred to as “modification reaction”) to the active terminal of the second conjugated diene polymer using a second alkoxysilane compound. It is an ingredient. By mixing the component (B), it is possible to produce a modified conjugated diene polymer capable of producing a rubber product excellent in low heat build-up and low temperature characteristics without impairing processability.
  • modification reaction a second alkoxysilyl group
  • the component (B) preferably has a structural unit derived from at least one conjugated diene compound selected from the group consisting of 1,3-butadiene, isoprene, and 2,3-dimethyl-1,3-butadiene.
  • the second conjugated diene polymer is a polymer of a conjugated diene compound having a vinyl content of less than 10%, a cis 1,4-bond content of 75% or more, and an Mw of 10,000 to 150,000, have.
  • the vinyl content of the second conjugated diene polymer is less than 10%, preferably less than 5%, and more preferably less than 2%. If the vinyl content is 10% or more, mechanical properties such as wear resistance of the rubber product after vulcanization may be inferior.
  • the vinyl content can be easily adjusted by controlling the temperature of the polymerization reaction.
  • the cis 1,4-bond content of the second conjugated diene polymer is 75% or more, preferably 85% or more, and more preferably 90 to 99.9%.
  • the cis 1,4-bond content can be easily adjusted by controlling the temperature of the polymerization reaction.
  • the Mw of the second conjugated diene polymer is 10,000 to 150,000, preferably 10,000 to 100,000, and more preferably 20,000 to 80,000.
  • Mw is less than 10,000, mechanical properties such as wear resistance of the rubber product after vulcanization may be inferior.
  • workability may be inferior.
  • Mw can be easily adjusted by controlling the amount of catalyst used for the polymerization reaction.
  • the first and second conjugated diene polymers can be prepared by polymerizing a conjugated diene compound (hereinafter also referred to as “polymerization reaction”).
  • the polymerization reaction is preferably performed using a catalyst in the presence of a solvent.
  • the solvent may be an inert organic solvent.
  • saturated aliphatic hydrocarbons having 4 to 10 carbon atoms such as butane, pentane, hexane and heptane
  • saturated alicyclic hydrocarbons having 6 to 20 carbon atoms such as cyclopentane and cyclohexane
  • 1-butene, 2-butene and the like Monoolefins
  • aromatic hydrocarbons such as benzene, toluene, xylene
  • halogenated carbonization such as methylene chloride, chloroform, carbon tetrachloride, trichloroethylene, perchloroethylene, 1,2-dichloroethane, chlorobenzene, bromobenzene, chlorotoluene
  • concentration of the conjugated diene compound in the solvent is usually 5 to 50% by mass, preferably 7 to 35% by mass.
  • the temperature of the polymerization reaction is usually ⁇ 30 to 200 ° C., preferably 0 to 150 ° C.
  • the temperature of the polymerization reaction is usually ⁇ 30 to 200 ° C., preferably 0 to 150 ° C.
  • the conjugated diene compound is not particularly limited.
  • at least one conjugated diene compound selected from the group consisting of 1,3-butadiene, isoprene, and 2,3-dimethyl-1,3-butadiene is preferable.
  • the conjugated diene compound used to prepare the first conjugated diene polymer and the conjugated diene compound used to prepare the second conjugated diene polymer may be the same, It may be different.
  • the catalyst used for the polymerization reaction is preferably a catalyst having components (c) to (e) as main components.
  • the polymerization reaction may be carried out in the presence of hydrogen gas.
  • (C) component a rare earth element-containing compound corresponding to atomic numbers 57 to 71 in the periodic table, or a reaction product of a rare earth element-containing compound and a Lewis base (d) component; alumoxane and general formula (1): AlR 1 R 2 R Organoaluminum compound corresponding to at least one of the compounds represented by 3 (in the general formula (1), R 1 and R 2 each independently represent a hydrocarbon group having 1 to 10 carbon atoms or a hydrogen atom) , R 3 represents a hydrocarbon group having 1 to 10 carbon atoms, provided that R 3 may be the same as or different from R 1 or R 2 .
  • the component (c) is a rare earth element-containing compound corresponding to atomic numbers 57 to 71 in the periodic table, or a reaction product of a rare earth element-containing compound and a Lewis base.
  • Examples of rare earth elements corresponding to atomic numbers 57 to 71 in the periodic table include neodymium, praseodymium, cerium, lanthanum, and gadolinium. Among these, neodymium is preferable.
  • the rare earth element-containing compound includes a rare earth element carboxylate, a rare earth element alkoxide, a rare earth element ⁇ -diketone complex, a rare earth element phosphate, or a rare earth element phosphate.
  • rare earth element carboxylates examples include compounds represented by the general formula (2): (R 4 —CO 2 ) 3 M.
  • M represents a rare earth element corresponding to atomic numbers 57 to 71 in the periodic table, and R 4 represents a hydrocarbon group having 1 to 20 carbon atoms.
  • the hydrocarbon group having 1 to 20 carbon atoms represented by R 4 is preferably a linear, branched or cyclic, saturated or unsaturated alkyl group.
  • Specific examples of the group represented by R 4 —CO 2 include octanoic acid, 2-ethylhexanoic acid, oleic acid, stearic acid, benzoic acid, naphthenic acid, versatic acid (trade names manufactured by Shell Chemical Co., Ltd.). And a carboxylic acid in which a carboxyl group is bonded to a tertiary carbon atom). Of these, 2-ethylhexanoic acid, naphthenic acid, and versatic acid are preferred.
  • the carboxyl group is bonded to a primary, secondary or tertiary carbon atom.
  • the rare earth element alkoxide for example, there is a compound represented by the general formula (3) :( R 5 O) 3 M.
  • M represents a rare earth element corresponding to atomic numbers 57 to 71 in the periodic table, and R 5 represents a hydrocarbon group having 1 to 20 carbon atoms.
  • the hydrocarbon group having 1 to 20 carbon atoms represented by R 5 is preferably a linear, branched or cyclic, saturated or unsaturated alkyl group.
  • Specific examples include 2-ethylhexyl group, oleyl group, stearyl group, phenyl group, and benzyl group. Among these, a 2-ethylhexyl group and a benzyl group are preferable.
  • ⁇ -diketone complexes of rare earth element ⁇ -diketone complexes include acetylacetone complexes, benzoylacetone complexes, propionylacetone complexes, valerylacetone complexes, and ethylacetylacetone complexes.
  • an acetylacetone complex and an ethylacetylacetone complex are preferable.
  • phosphoric acid or phosphorous acid of rare earth element phosphates or rare earth element phosphites include bis (2-ethylhexyl) phosphate, bis (1-methylheptyl) phosphate, and bisphosphate.
  • bis (2-ethylhexyl) phosphate bis (1-methylheptyl) phosphate, mono-2-ethylhexyl 2-ethylhexylphosphonate, and bis (2-ethylhexyl) phosphinic acid are preferable.
  • neodymium phosphate or neodymium carboxylate is particularly preferred, and neodymium carboxylate such as 2-ethylhexanoate or versatic acid salt is most preferred.
  • a Lewis base is used to easily solubilize a rare earth element-containing compound in a solvent.
  • a solvent for example, acetylacetone, tetrahydrofuran, pyridine, N, N-dimethylformamide, thiophene, diphenyl ether, triethylamine, an organic phosphorus compound, 1
  • divalent or divalent alcohols for example, acetylacetone, tetrahydrofuran, pyridine, N, N-dimethylformamide, thiophene, diphenyl ether, triethylamine, an organic phosphorus compound, 1
  • divalent or divalent alcohols for example, acetylacetone, tetrahydrofuran, pyridine, N, N-dimethylformamide, thiophene, diphenyl ether, triethylamine, an organic phosphorus compound, 1
  • divalent or divalent alcohols for example, acetylacetone, tetrahydr
  • the amount of Lewis base used is usually 0 to 30 mol, preferably 1 to 10 mol, per mol of the rare earth element compound.
  • the reaction product may be prepared and used in a polymerization reaction system, or may be separately prepared and used in advance.
  • the amount of the component (c) is preferably 0.00001 to 1.0 mmol with respect to 100 g of the conjugated diene compound. More preferably, it is 0.5 mmol.
  • the amount of component (c) used is less than 0.00001 mmol, the polymerization activity may be low.
  • it exceeds 1.0 mmol the catalyst concentration becomes high, so that a decontacting step may be required.
  • the component (d) is an organoaluminum compound corresponding to at least one of the alumoxane and the compound represented by the general formula (1): AlR 1 R 2 R 3 .
  • R 1 and R 2 each independently represent a hydrocarbon group having 1 to 10 carbon atoms or a hydrogen atom
  • R 3 represents a hydrocarbon group having 1 to 10 carbon atoms.
  • R 3 may be the same as or different from R 1 or R 2.
  • alumoxane examples include compounds having a structure represented by the general formula (4) or (5), fine chemicals, 23, (9), 5 (1994), J. Org. Am. Chem. Soc. 115, 4971 (1993); Am. Chem. Soc. 117, 6465 (1995).
  • R 6 independently represents a hydrocarbon group having 1 to 20 carbon atoms, and n represents an integer of 2 or more.
  • the hydrocarbon group having 1 to 20 carbon atoms represented by R 6 is specifically a methyl group, an ethyl group, a propyl group, a butyl group, an isobutyl group, t- A butyl group, a hexyl group, an isohexyl group, an octyl group, an isooctyl group, etc. can be mentioned.
  • a methyl group, an ethyl group, an isobutyl group, and a t-butyl group are preferable, and a methyl group is particularly preferable.
  • N is an integer of 2 or more, preferably an integer of 4 to 100.
  • alumoxane examples include methylalumoxane, ethylalumoxane, n-propylalumoxane, n-butylalumoxane, isobutylalumoxane, t-butylalumoxane, hexylalumoxane, isohexylalumoxane, and the like. Can do.
  • the alumoxane may be prepared using any known technique. For example, trialkylaluminum or dialkylaluminum monochloride is added to an organic solvent such as benzene, toluene, xylene, and water, water vapor, water vapor-containing nitrogen gas, or copper sulfate pentahydrate or aluminum sulfate 16 hydrate. It can be prepared by adding a salt having water of crystallization and reacting. In addition, alumoxane may be used individually by 1 type and may be used in combination of 2 or more type.
  • AlR 1 R 2 R 3 include trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutyl.
  • an organic aluminum compound may be used individually by 1 type, and may be used in combination of 2 or more type.
  • the use ratio of the component (d) can be generally expressed as a molar ratio of Al to the component (c).
  • the Mw of the conjugated diene polymer can be controlled by appropriately setting the use ratio of the component (d).
  • the molar ratio ((c) :( d)) of the component (c) to the component (d) is usually 1: 1 to 1: 500, preferably 1: 3 to 1: 250, More preferably, it is 5 to 1: 200. Outside these ranges, it is not preferable because it does not act as a highly active catalyst or requires a decontacting step.
  • Component is a halogen-containing compound.
  • the halogen-containing compound include a reaction product of a metal halide and a Lewis base, diethylaluminum chloride, silicon tetrachloride, trimethylchlorosilane, methyldichlorosilane, dimethyldichlorosilane, methyltrichlorosilane, ethylaluminum dichloride, ethylaluminum sesquioxide.
  • metal halide examples include beryllium chloride, beryllium bromide, beryllium iodide, magnesium chloride, magnesium bromide, magnesium iodide, calcium chloride, calcium bromide, calcium iodide, barium chloride, barium bromide and iodide.
  • examples of the Lewis base include phosphorus compounds, carbonyl compounds, nitrogen compounds, ether compounds, alcohols, and the like.
  • phosphorus compounds such as tributyl phosphate, tri-2-ethylhexyl phosphate, triphenyl phosphate, tricresyl phosphate, triethylphosphine, tributylphosphine, triphenylphosphine, diethylphosphinoethane, diphenylphosphinoethane, and the like; Acetylacetone, benzoylacetone, propionitrile acetone, valeryl acetone, ethyl acetylacetone, methyl acetoacetate, ethyl acetoacetate, phenyl acetoacetate, dimethyl malonate, diethyl malonate, diphenyl malonate, acetic acid, octanoic acid, 2-ethylhexane Carbon
  • tri-2-ethylhexyl phosphate, tricresyl phosphate, acetylacetone, 2-ethylhexanoic acid, versatic acid, 2-ethylhexyl alcohol, 1-decanol, and lauryl alcohol are preferable.
  • the amount of Lewis base used is usually 0.01 to 30 mol, preferably 0.5 to 10 mol, per mol of metal halide. When the reaction product of the metal halide and the Lewis base is used, the amount of metal remaining in the conjugated diene polymer can be reduced.
  • the use ratio of the (e) component can be expressed by the molar ratio of the (c) component and the (e) component.
  • the molar ratio of component (c) to component (e) ((c) :( e)) is usually 1: 0.1 to 1:30 and should be 1: 0.2 to 1:15. preferable. Outside these ranges, it is not preferable because it does not act as a highly active catalyst or requires a decontacting step.
  • a conjugated diene compound and a non-conjugated diene compound (also referred to as “other components” in the present specification) is used. ) You may use it in the ratio of 0-1000 mol per 1 mol of components.
  • the conjugated diene compound used as the other component 1,3-butadiene, isoprene, or the like can be used as in the conjugated diene compound used in the polymerization reaction.
  • non-conjugated diene compound examples include divinylbenzene, diisopropenylbenzene, triisopropenylbenzene, 1,4-vinylhexadiene, and ethylidene norbornene.
  • Other components as the catalyst component are not essential, but when used together, there is an advantage that the catalytic activity is further improved.
  • the catalyst can be prepared, for example, by reacting the components (c) to (e) dissolved in a solvent and, if necessary, other components.
  • the addition order of each component may be arbitrary.
  • Each component is preferably mixed, reacted, and aged in advance from the viewpoint of improving the polymerization activity and shortening the polymerization initiation time.
  • the aging temperature is usually 0 to 100 ° C, preferably 20 to 80 ° C. If the aging temperature is less than 0 ° C., aging may not be performed sufficiently. On the other hand, if it exceeds 100 ° C., the catalyst activity may decrease and the molecular weight distribution may spread, which is not preferable.
  • the aging time is not particularly limited, and can be contacted in the line before being added to the polymerization reaction tank. Usually, 0.5 minutes or more is sufficient, and stable for several days.
  • the modification reaction is a reaction in which an alkoxysilyl group is introduced into the active terminal of the prepared conjugated diene polymer using a modifier. It is important to carry out the modification reaction after completion of the polymerization reaction and before performing various operations necessary for solvent removal treatment, water treatment, heat treatment, isolation of the conjugated diene polymer, and the like.
  • the modification reaction is preferably performed by a solution reaction (a solution containing an unreacted conjugated diene compound used in the polymerization reaction).
  • a solution reaction a solution containing an unreacted conjugated diene compound used in the polymerization reaction.
  • the type of the denaturation reaction is not particularly limited, and it may be performed using a batch reactor, or may be performed continuously using an apparatus such as a multistage continuous reactor or an inline mixer.
  • the conjugated diene polymer is preferably one in which at least 10% of the polymer chains have living properties.
  • the temperature of the modification reaction can be the temperature of the polymerization reaction. Specifically, 20 to 100 ° C. is preferable, and 40 to 90 ° C. is more preferable. When the temperature is less than 20 ° C., the modification reaction proceeds slowly, and the active terminal of the conjugated diene polymer may be deactivated. On the other hand, if it exceeds 100 ° C., the active terminal of the conjugated diene polymer tends to be deactivated, which is not preferable.
  • the reaction time for the modification reaction is usually 5 minutes to 5 hours, preferably 15 minutes to 1 hour.
  • the modifying agent is not particularly limited, but an alkoxysilane compound having at least one functional group selected from the group consisting of (f) to (h) is preferably used.
  • the modifier may be a partial condensate or a mixture of a modifier and a partial condensate.
  • the “partial condensate” herein refers to a product in which a part (not all) of the modifier SiOR is bonded to SiOSi by condensation.
  • the first alkoxysilane compound and the second alkoxysilane compound may be the same or different.
  • F epoxy group
  • g isocyanate group
  • epoxy group-containing alkoxysilane compounds specifically, 2-glycidoxyethyltrimethoxysilane, 2-glycidoxyethyltriethoxysilane, (2-glycidoxyethyl) methyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, (3-glycidoxypropyl) methyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- ( Examples include 3,4-epoxycyclohexyl) ethyltriethoxysilane and 2- (3,4-epoxycyclohexyl) ethyl (methyl) dimethoxysilane. Among these, 3-glycidoxypropyltrimethoxysilane and 2- (3,4-epoxycyclohexyl) ethyl (methyl) dime
  • isocyanate group-containing alkoxysilane compound examples include 3-isocyanatepropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-isocyanatopropylmethyldiethoxysilane, 3-isocyanatopropyltriisopropoxysilane, and the like. Can be mentioned. Of these, 3-isocyanatopropyltrimethoxysilane is preferred.
  • acyl group-containing alkoxysilane compound specifically, 3-methacryloyloxypropyltriethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropylmethyldiethoxysilane, 3-methacryloyl Roxypropyltriisopropoxysilane and the like can be mentioned. Among these, 3-methacryloyloxypropyltrimethoxysilane is preferable.
  • denaturant may be used individually by 1 type and may be used in combination of 2 or more type.
  • the amount of the modifying agent used is preferably 0.000001 to 0.01, more preferably 0.00001 to 0.001, in terms of a molar ratio to the conjugated diene polymer. If the amount used is less than 0.000001, the modification reaction may not proceed sufficiently and the dispersibility of the filler may not be sufficiently improved. On the other hand, if it exceeds 0.01, the modification reaction is sufficiently saturated, which is not economical.
  • the addition method of the modifier is not particularly limited, and includes a batch addition method, a division addition method, a continuous addition method, and the like. Among these, the method of adding all at once is preferable. After the modification, conventionally known post-treatment can be performed to obtain the component (A) and the component (B).
  • mixture The method of mixing is not particularly limited, and for example, the mixing can be performed by adding the solution of component (B) to the prepared solution of component (A) and then stirring.
  • Condensation reaction After mixing the component (A) and the component (B), a modified conjugated diene polymer can be produced by condensing the first alkoxysilyl group and the second alkoxysilyl group introduced into each component. . In the condensation reaction, the first alkoxysilyl groups and the second alkoxysilyl groups may condense. Therefore, the modified conjugated diene polymer is produced as a mixture thereof.
  • Condensation reaction is performed in an aqueous solution.
  • the temperature for the condensation reaction is usually 85 to 180 ° C, preferably 100 to 170 ° C, and more preferably 110 to 150 ° C. If the temperature is lower than 85 ° C., the condensation reaction proceeds slowly, and the reaction may not be completed, and the (A) component or the (B) component may change over time, resulting in quality problems. is there. On the other hand, if it exceeds 180 ° C., the physical properties may be lowered, which is not preferable.
  • the pH value of the aqueous solution is usually 9 to 14, and preferably 10 to 12. If the pH value is less than 9, the progress of the condensation reaction is slow, and the reaction may not be completed. Therefore, the (A) component or the (B) component changes with time, resulting in quality problems. There is a case.
  • the reaction time is usually 5 minutes to 10 hours, preferably about 15 minutes to 5 hours. If the reaction time is less than 5 minutes, the condensation reaction may not proceed sufficiently. On the other hand, if it exceeds 10 hours, the condensation reaction is saturated, which is not economically preferable.
  • the pressure in the reaction system during the condensation reaction is usually 0.01 to 20 MPa, and preferably 0.05 to 10 MPa.
  • the form of the condensation reaction is not particularly limited, and may be performed using a batch reactor, or may be performed continuously using an apparatus such as a multistage continuous reactor. Further, the condensation reaction and the solvent removal may be performed simultaneously.
  • condensation accelerator At least one of the components (a) and (b) (hereinafter also referred to as “condensation accelerator”). This is used to promote the condensation reaction between the first alkoxysilyl group and the second alkoxysilyl group.
  • component compound containing at least one element selected from the group consisting of titanium (Ti), zirconium (Zr), bismuth (Bi), aluminum (Al), and tin (Sn)
  • component component
  • the condensation accelerator can be added after the condensation reaction, but is preferably added before the condensation reaction. When added after the start of the condensation reaction, the condensation accelerator may not be uniformly dispersed, and the catalyst performance may be lowered.
  • the addition time of the condensation accelerator is usually 5 minutes to 5 hours before the start of the condensation reaction, and preferably 15 minutes to 1 hour before.
  • the component (a) is a compound containing at least one element selected from the group consisting of titanium (Ti), zirconium (Zr), bismuth (Bi), aluminum (Al), and tin (Sn).
  • the compound containing titanium (Ti) include tetramethoxy titanium, tetraethoxy titanium, tetra n-propoxy titanium, tetra i-propoxy titanium, tetra n-butoxy titanium, tetra n-butoxy titanium oligomer, tetra sec -Butoxytitanium, tetra-tert-butoxytitanium, tetra (2-ethylhexyl) titanium, bis (octanediolate) bis (2-ethylhexyl) titanium, tetra (octanediolate) titanium, titanium lactate, titanium dipropoxybis (triethanol Aminate), titanium dibutoxybis (triethanolaminate), titanium tributoxy systemate, titanium tripropoxy systemate, titanium Tripropoxyacetylacetonate, titanium dipropoxybis (acetylacetonate), titanium tripropoxyethylacetoacetate, titaniumpropoxyacetylacet
  • Zr zirconium
  • Specific examples of the compound containing zirconium (Zr) include tetraethoxyzirconium, tetran-propoxyzirconium, tetrai-propoxyzirconium, tetran-butoxyzirconium, tetrasec-butoxyzirconium, tetratert-butoxyzirconium.
  • bismuth bismuth (Bi)
  • bismuth specifically, tris (2-ethylhexanoate) bismuth, tris (laurate) bismuth, tris (naphthate) bismuth, tris (stearate) bismuth, tris (oleate) ) Bismuth, tris (linoleate) bismuth and the like.
  • Specific examples of the compound containing aluminum (Al) include triethoxyaluminum, tri-n-propoxyaluminum, tri-i-propoxyaluminum, tri-n-butoxyaluminum, trisec-butoxyaluminum, and tritert-butoxyaluminum.
  • Tri (2-ethylhexyl) aluminum aluminum dibutoxy systemate, aluminum dibutoxyacetylacetonate, aluminum butoxybis (acetylacetonate), aluminum dibutoxyethylacetoacetate, aluminum tris (acetylacetonate), aluminum tris (ethyl) Acetoacetate), tris (2-ethylhexanoate) aluminum, tris (laurate) aluminum, tris (naphthate) al Bromide, tris (stearate) aluminum, tris (oleate) aluminum, can be mentioned tris (linolate) aluminum and the like.
  • tin (Sn) specifically, bis (n-octanoate) tin, bis (2-ethylhexanoate) tin, bis (laurate) tin, bis (naphthoenate) tin, bis (Stearate) tin, bis (oleate) tin, dibutyltin diacetate, dibutyltin di-n-octanoate, dibutyltin di-2-ethylhexanoate, dibutyltin dilaurate, dibutyltin malate, dibutyltin bis (benzylmalate), dibutyltin bis (2 -Ethylhexyl malate), di-n-octyltin diacetate, di-n-octyltin di-n-octanoate, di-n-octyltin di-2-ethylhexanoate
  • the component is a carboxylic acid partial ester of a polyhydric alcohol.
  • Specific examples include sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan tristearate, sorbitan monooleate, sorbitan trioleate, and the like.
  • the molar ratio of the compound to the total amount of alkoxysilyl groups present in the reaction system is preferably 0.1 to 10, and particularly preferably 0.5 to 5. If the molar ratio is less than 0.1, the condensation reaction may not proceed sufficiently. On the other hand, if it exceeds 10, it is not economically preferable.
  • Modified conjugated diene polymer The modified conjugated diene polymer of the present invention is obtained by “I. Method for producing modified conjugated diene polymer”.
  • the Mooney viscosity (ML 1 + 4 , 125 ° C.) of the modified conjugated diene polymer is preferably 20 to 80, and more preferably 30 to 50. If the Mooney viscosity is less than 20, the physical properties of rubber such as fracture characteristics tend to decrease, which is not preferable. On the other hand, when it exceeds 80, workability is deteriorated and it may be difficult to knead with the compounding agent.
  • the rubber composition of the present invention contains a rubber component containing the modified conjugated diene polymer described in “II. Modified conjugated diene polymer”. Further, it is preferable that the filler contains 20 to 120 parts by mass with respect to 100 parts by mass of the rubber component.
  • the modified conjugated diene polymer contained in the rubber component is a modified conjugated diene polymer described in “II. Modified Conjugated Diene Polymer”.
  • the content of the modified conjugated diene polymer is preferably 20% by mass or more, more preferably 30% by mass or more, and particularly preferably 40% by mass or more. When the content ratio is less than 20% by mass, the low heat build-up property, the low temperature characteristics, etc. may be deteriorated.
  • Rubber Rubbers included in the rubber component are natural rubber, synthetic isoprene rubber, butadiene rubber, styrene / butadiene rubber, ethylene / ⁇ -olefin copolymer rubber, ethylene / ⁇ -olefin / diene copolymer rubber, acrylonitrile / butadiene. It is preferably at least one selected from the group consisting of copolymer rubber, chloroprene rubber, and halogenated butyl rubber. These may use what was prepared in accordance with the conventionally well-known method, and may use what is marketed.
  • the rubber content is preferably 80% by mass or less, more preferably 70% by mass or less, and particularly preferably 60% by mass or less. When the content ratio is more than 80% by mass, low heat build-up, low temperature characteristics, etc. may deteriorate.
  • the filler is preferably at least one of silica and carbon black.
  • the amount of the filler used is usually 20 to 120 parts by weight, preferably 30 to 100 parts by weight, and more preferably 35 to 90 parts by weight with respect to 100 parts by weight of the rubber component. If the amount used is less than 20 parts by mass, the effect of containing a filler may not be sufficiently exhibited. On the other hand, if it exceeds 120 parts by mass, the processability of the rubber composition may deteriorate.
  • Silica Silica is not particularly limited, and examples thereof include wet silica (hydrous silicic acid), dry silica (anhydrous silicic acid), calcium silicate, and aluminum silicate. Among these, wet silica is most preferred because it has the most remarkable effects of improving fracture resistance, wet grip properties and low rolling resistance, and low-temperature properties.
  • silane coupling agent When silica is used as the filler, a silane coupling agent can be blended for the purpose of further improving the reinforcement.
  • the silane coupling agent include bis (3-triethoxysilylpropyl) tetrasulfide, bis (3-triethoxysilylpropyl) trisulfide, bis (3-triethoxysilylpropyl) disulfide, and bis (2-triethoxy).
  • Ethoxysilylethyl) tetrasulfide bis (3-trimethoxysilylpropyl) tetrasulfide, bis (2-trimethoxysilylethyl) tetrasulfide, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 2-mercapto Ethyltrimethoxysilane, 2-mercaptoethyltriethoxysilane, 3-trimethoxysilylpropyl-N, N-dimethylthiocarbamoyl tetrasulfide, 3-triethoxysilylpropyl-N, N-dimethylthio Rubamoyl tetrasulfide, 2-triethoxysilylethyl-N, N-dimethylthiocarbamoyl tetrasulfide, 3-trimethoxysilylpropylbenzothiazolyl tetra
  • bis (3-triethoxysilylpropyl) polysulfide and 3-trimethoxysilylpropylbenzothiazyl tetrasulfide are preferable from the viewpoint of improving the reinforcing property.
  • these silane coupling agents may be used individually by 1 type, and may be used in combination of 2 or more type.
  • the rubber component contains a modified conjugated diene polymer in which an alkoxysilyl group having a high affinity with silica is introduced at the molecular terminal, so the blending amount of the silane coupling agent Can be reduced more than usual.
  • the blending ratio of the silane coupling agent varies depending on the type of the silane coupling agent and the like, but is preferably 1 to 20% by mass, more preferably 3 to 15% by mass with respect to silica. If the blending ratio is less than 1% by mass, the effect is not sufficiently exhibited. On the other hand, if it exceeds 20% by mass, the rubber component may be gelled.
  • Carbon black is not particularly limited, and examples thereof include SRF, GPF, FEF, HAF, ISAF, and SAF.
  • carbon black having an iodine adsorption amount (IA) of 60 mg / g or more and a dibutyl phthalate oil absorption (DBP) of 80 mL / 100 g or more is preferable, and HAF, ISAF, and SAF having excellent wear resistance are particularly preferable.
  • the rubber composition of the present invention is a kneading machine such as an open kneading machine such as a roll or a closed kneading machine such as a Banbury mixer with a rubber component containing the modified conjugated diene polymer of the present invention, if necessary. It can manufacture by kneading
  • the tire of the present invention uses the rubber composition described in “III. Rubber composition”. Therefore, the workability is not impaired, the productivity is excellent, and the performance required for the tire such as low heat generation, low temperature characteristics, and wear resistance is also excellent.
  • Mw / Mn Weight average molecular weight (Mw) and number average molecular weight (Mn) measured under the following conditions using a differential refractometer as a detector using HLC-8120GPC manufactured by Tosoh Corporation It was calculated from the value of Column: manufactured by Tosoh Corporation, column GMHHXL Mobile phase; tetrahydrofuran Column temperature; 40 ° C
  • Example 1- (A) (Preparation of Component (A) of Modified Conjugated Diene Polymer A) A nitrogen-substituted 5 L autoclave was charged with 2.4 kg of cyclohexane and 300 g of 1,3-butadiene under a nitrogen atmosphere.
  • a cyclohexane solution of neodymium versatate (hereinafter also referred to as “NdVer”) (0.09 mmol)
  • a toluene solution of methylalumoxane (hereinafter also referred to as “MAO”) (1.8 mmol)
  • hydrogen Diisobutylaluminum fluoride (hereinafter also referred to as “DIBAH”) (4.7 mmol) and diethylaluminum chloride (hereinafter also referred to as “DEAC”) (0.18 mmol) in toluene solution and 1,3-butadiene (4.5 mmol)
  • DIBAH Diisobutylaluminum fluoride
  • DEAC diethylaluminum chloride
  • the reaction conversion of 1,3-butadiene was almost 100%.
  • 200 g of this polymer solution was extracted, a methanol solution containing 1.5 g of 2,4-di-tert-butyl-p-cresol was added to stop the polymerization reaction, and the solvent was removed by steam stripping at 110 ° C.
  • the first conjugated diene polymer (1) was obtained by drying with a roll.
  • the obtained first conjugated diene polymer (1) had an Mw of 353,000, a cis 1,4-bond content of 96.8%, and a vinyl content of 1.1%.
  • a toluene solution of 3-glycidoxypropyltrimethoxysilane (hereinafter also referred to as “GPMOS”) (4.5 mmol) was added, and a denaturation reaction was performed for 30 minutes. It was. Thereafter, a methanol solution containing 1.5 g of 2,4-di-tert-butyl-p-cresol was added to obtain 2.5 kg of component (A) of the modified conjugated diene polymer A.
  • GMOS 3-glycidoxypropyltrimethoxysilane
  • Example 1- (Preparation of Component (B) of Modified Conjugated Diene Polymer A) A nitrogen-substituted 5 L autoclave was charged with 2.4 kg of cyclohexane and 300 g of 1,3-butadiene under a nitrogen atmosphere. Separately, a cyclohexane solution of NdVer (0.09 mmol), a toluene solution of MAO (1.8 mmol), a toluene solution of DIBAH (14.8 mmol) and DEAC (0.18 mmol), and 1,3-butadiene A catalyst prepared by reaction aging (4.5 mmol) at 50 ° C. for 30 minutes was charged, and polymerization was performed at 80 ° C.
  • the reaction conversion of 1,3-butadiene was almost 100%.
  • 200 g of this polymer solution was extracted, a methanol solution containing 1.5 g of 2,4-di-tert-butyl-p-cresol was added to stop the polymerization reaction, and the solvent was removed by steam stripping at 110 ° C.
  • the second conjugated diene polymer (1) was obtained by drying with a roll.
  • the obtained second conjugated diene polymer (1) had an Mw of 71,000, a cis 1,4-bond content of 94.5%, and a vinyl content of 1.1%.
  • the remaining polymer solution was kept at a temperature of 60 ° C., a toluene solution of GPMOS (4.5 mmol) was added, and a denaturation reaction was performed for 30 minutes. Thereafter, a methanol solution containing 1.5 g of 2,4-di-tert-butyl-p-cresol was added to obtain 2.5 kg of component (B) of the modified conjugated diene polymer A.
  • Example 1- (C) (Production of Modified Conjugated Diene Polymer A)
  • Example 1 630 g of the (A) component of the modified conjugated diene polymer A obtained in (A) and 270 g of the (B) component of the modified conjugated diene polymer A obtained in Example 1- (B)
  • the mixed solution is added to 10 L of an aqueous solution adjusted to pH 10 with sodium hydroxide, subjected to a condensation reaction with solvent removal at 110 ° C. for 2 hours, dried with a roll at 110 ° C., and modified conjugated diene polymer A Manufactured.
  • the Mooney viscosity (ML 1 + 4 , 125 ° C.) of the modified conjugated diene polymer A was 38.
  • Example 2- (A) (Preparation of Component (A) of Modified Conjugated Diene Polymer B) In Example 1- (A), except that the DIBAH usage was changed to 4.3 mmol, the modified conjugated diene polymer B (A) was prepared by the same charging composition and polymerization method as in Example 1- (A). ) Component was obtained.
  • the physical property values of the first conjugated diene polymer (2) after the polymerization reaction are shown in Table 1.
  • Example 2- (B) (Preparation of Component (B) of Modified Conjugated Diene Polymer B) In Example 1- (B), except that the amount of DIBAH used was changed to 27.4 mmol, the modified conjugated diene polymer B of (B ) Component was obtained.
  • the physical property values of the second conjugated diene polymer (2) after the polymerization reaction are shown in Table 1.
  • Example 2- (C) (Production of Modified Conjugated Diene Polymer B)
  • Example 2- 720 g of component (A) of modified conjugated diene polymer B obtained in (A) and 180 g of component (B) of modified conjugated diene polymer B obtained in Example 2- (B) Mix for 30 minutes at room temperature. Subsequently, a toluene solution of tetraisopropyl titanate (hereinafter also referred to as “IPOTi”) (13.5 mmol) was added and mixed for 30 minutes. Next, the mixed solution is added to 10 L of an aqueous solution adjusted to pH 10 with sodium hydroxide, subjected to a condensation reaction with solvent removal at 110 ° C.
  • IPTTi tetraisopropyl titanate
  • modified conjugated diene polymer B Manufactured.
  • the Mooney viscosity (ML 1 + 4 , 125 ° C.) of the modified conjugated diene polymer B was 41.
  • Example 3- (Preparation of Component (A) of Modified Conjugated Diene Polymer C)
  • the modified conjugated diene polymer C (A) was prepared by the same charging composition and polymerization method as Example 1- (A).
  • Component was obtained.
  • Table 1 shows the physical property values of the first conjugated diene polymer (3) after the polymerization reaction.
  • Example 3- (B) (Preparation of Component (B) of Modified Conjugated Diene Polymer C)
  • Example 1 Component (B) of modified conjugated diene polymer B was obtained by the same charging composition and polymerization method as in (B).
  • the physical property values of the second conjugated diene polymer (3) after the polymerization reaction are shown in Table 1.
  • Example 3- (Production of Modified Conjugated Diene Polymer C)
  • Example 3- 675 g of the (A) component of the modified conjugated diene polymer C obtained in (A) and 225 g of the (B) component of the modified conjugated diene polymer B obtained in Example 3- (B) Were mixed for 30 minutes at room temperature. Subsequently, a toluene solution of tris (2-ethylhexanoate) bismuth (hereinafter also referred to as “EHABi”) (13.5 mmol) was added and mixed for 30 minutes.
  • EHABi tris (2-ethylhexanoate) bismuth
  • the mixed solution is added to 10 L of an aqueous solution adjusted to pH 10 with sodium hydroxide, subjected to a condensation reaction with solvent removal at 110 ° C. for 2 hours, dried with a roll at 110 ° C., and modified conjugated diene polymer C Manufactured.
  • the Mooney viscosity (ML 1 + 4 , 125 ° C.) of the modified conjugated diene polymer C was 46.
  • Example 4- (A) (Preparation of Component (A) of Modified Conjugated Diene Polymer D) In Example 1- (A), except that the amount of DIBAH used was changed to 4.8 mmol, the modified conjugated diene polymer D (A ) Component was obtained.
  • the physical property values of the first conjugated diene polymer (4) after the polymerization reaction are shown in Table 1.
  • Example 4- (B) (Preparation of Component (B) of Modified Conjugated Diene Polymer D) In Example 1- (B), except that the amount of DIBAH used was changed to 8.8 mmol, the modified conjugated diene polymer D of (B ) Component was obtained.
  • the physical property values of the second conjugated diene polymer (4) after the polymerization reaction are shown in Table 1.
  • Example 4- (C) (Production of Modified Conjugated Diene Polymer D)
  • Example 4- (A) component 765 g of the modified conjugated diene polymer D obtained in (A) and 135 g of the component (B) of the modified conjugated diene polymer D obtained in Example 4- (B) Were mixed for 30 minutes at room temperature. Subsequently, a toluene solution of bis (2-ethylhexanoate) zirconium oxide (hereinafter also referred to as “EHAZrO”) (13.5 mmol) was added and mixed for 30 minutes.
  • EHAZrO bis (2-ethylhexanoate) zirconium oxide
  • the mixed solution is added to 10 L of an aqueous solution adjusted to pH 10 with sodium hydroxide, subjected to a condensation reaction with solvent removal at 110 ° C. for 2 hours, dried with a roll at 110 ° C., and modified conjugated diene polymer D Manufactured.
  • the Mooney viscosity (ML 1 + 4 , 125 ° C.) of the modified conjugated diene polymer D was 39.
  • Example 5- (Preparation of Component (A) of Modified Conjugated Diene Polymer E)
  • the modified conjugated diene polymer E (A) was prepared by the same charging composition and polymerization method as in Example 1- (A) except that the amount of DIBAH used in Example 1- (A) was changed to 4.6 mmol. ) Component was obtained.
  • the physical property values of the first conjugated diene polymer (5) after the polymerization reaction are shown in Table 1.
  • Example 5- (B) (Preparation of Component (B) of Modified Conjugated Diene Polymer E)
  • Example 1 Component (B) of modified conjugated diene polymer E was obtained by the same charging composition and polymerization method as in (B).
  • the physical property values of the second conjugated diene polymer (5) after the polymerization reaction are shown in Table 1.
  • Example 5- (C) (Production of Modified Conjugated Diene Polymer E) 675 g of the component (A) of the modified conjugated diene polymer E obtained in Example 5- (A) and 225 g of the component (B) of the modified conjugated diene polymer E obtained in Example 5- (B) Were mixed for 30 minutes at room temperature. Subsequently, a toluene solution of tris (2-ethylhexanoate) aluminum (hereinafter also referred to as “EHAAl”) (13.5 mmol) was added and mixed for 30 minutes. Next, the mixed solution is added to 10 L of an aqueous solution adjusted to pH 10 with sodium hydroxide, subjected to a condensation reaction with solvent removal at 110 ° C.
  • EHAAl tris (2-ethylhexanoate) aluminum
  • modified conjugated diene polymer E Manufactured.
  • the Mooney viscosity (ML 1 + 4 , 125 ° C.) of the modified conjugated diene polymer E was 37.
  • Example 6- (Preparation of Component (A) of Modified Conjugated Diene Polymer F)
  • the modified conjugated diene polymer F (A) was prepared by the same charging composition and polymerization method as Example 1- (A).
  • Component was obtained.
  • the physical property values of the first conjugated diene polymer (6) after the polymerization reaction are shown in Table 1.
  • Example 6- (B) (Preparation of Component (B) of Modified Conjugated Diene Polymer F)
  • Example 1 Component (B) of modified conjugated diene polymer F was obtained by the same charging composition and polymerization method as in (B).
  • the physical property values of the second conjugated diene polymer (6) after the polymerization reaction are shown in Table 1.
  • Example 6- (C) (Production of Modified Conjugated Diene Polymer F)
  • Example 6- (A) component 630 g of the modified conjugated diene polymer F obtained in (A) and 270 g of the component (B) of the modified conjugated diene polymer F obtained in Example 6- (B) Were mixed for 30 minutes at room temperature. Subsequently, a toluene solution of bis (2-ethylhexanoate) tin (hereinafter also referred to as “EHASn”) (13.5 mmol) was added and mixed for 30 minutes. Next, the mixed solution is added to 10 L of an aqueous solution adjusted to pH 10 with sodium hydroxide, subjected to a condensation reaction with solvent removal at 110 ° C.
  • EHASn bis (2-ethylhexanoate
  • modified conjugated diene polymer F Manufactured.
  • the Mooney viscosity (ML 1 + 4 , 125 ° C.) of the modified conjugated diene polymer F was 52.
  • Example 7- (A) (Preparation of Component (A) of Modified Conjugated Diene Polymer G)
  • Example 1- Example 1- (A), except that DIBAH usage was 3.6 mmol and GPMOS was replaced with 3-isocyanatopropyltriethoxysilane (hereinafter also referred to as “IPEOS”).
  • the component (A) of the modified conjugated diene polymer G was obtained by the same charging composition and polymerization method.
  • Table 1 shows the physical property values of the first conjugated diene polymer (7) after the polymerization reaction.
  • Example 7- (B) (Preparation of Component (B) of Modified Conjugated Diene Polymer G)
  • the component (B) of the modified conjugated diene polymer G was obtained by the same charging composition and polymerization method as in Example 1- (B), except that GPMOS was replaced with IPEOS. It was.
  • the physical property values of the second conjugated diene polymer (7) after the polymerization reaction are shown in Table 1.
  • Example 7- (C) (Production of Modified Conjugated Diene Polymer G)
  • STO sorbitan acid trioleate
  • modified conjugated diene polymer G Manufactured.
  • the Mooney viscosity (ML 1 + 4 , 125 ° C.) of the modified conjugated diene polymer G was 42.
  • Example 8- (A) (Preparation of Component (A) of Modified Conjugated Diene Polymer H)
  • Example 1- (A) Except that DIBAH usage was changed to 3.4 mmol and GPMOS was replaced with 3-isocyanatopropyltriethoxysilane (hereinafter also referred to as “IPEOS”) in Example 1-
  • IPEOS 3-isocyanatopropyltriethoxysilane
  • Table 1 shows the physical property values of the first conjugated diene polymer (8) after the polymerization reaction.
  • Example 8- (B) (Preparation of Component (B) of Modified Conjugated Diene Polymer H)
  • Example 7- Component (B) of modified conjugated diene polymer H was obtained by the same charging composition and polymerization method as in (B).
  • the physical property values of the second conjugated diene polymer (8) after the polymerization reaction are shown in Table 1.
  • Example 8- (C) (Production of Modified Conjugated Diene Polymer H)
  • Example 8- (A) component 630 g of the modified conjugated diene polymer H obtained in (A) and 270 g of the component (B) of the modified conjugated diene polymer H obtained in Example 8- (B) Were mixed for 30 minutes at room temperature. Subsequently, a toluene solution of sorbitan acid monolaurate (hereinafter also referred to as “SML”) (135 mmol) was added and mixed for 30 minutes. Next, the mixed solution is added to 10 L of an aqueous solution adjusted to pH 10 with sodium hydroxide, subjected to a condensation reaction with solvent removal at 110 ° C.
  • SML sorbitan acid monolaurate
  • modified conjugated diene polymer H Manufactured.
  • the Mooney viscosity (ML 1 + 4 , 125 ° C.) of the modified conjugated diene polymer H was 45.
  • Example 1 (Production of Modified Conjugated Diene Polymer I) A modified conjugated diene polymer I was obtained by the same charging composition and polymerization method as in Example 1- (A) except that the amount of DIBAH used in Example 1- (A) was changed to 5.0 mmol. .
  • the physical property values of the first conjugated diene polymer (9) are shown in Table 1.
  • Example 1- (A) A modified conjugated diene polymer J was obtained by the same charging composition and polymerization method.
  • the physical property values of the first conjugated diene polymer (10) are shown in Table 1.
  • Example 3 (Production of Modified Conjugated Diene Polymer K)
  • the amount of DIBAH used was 5.0 mmol, and a toluene solution of EHASn (13.5 mmol) was added during the condensation reaction and mixed for 30 minutes.
  • a modified conjugated diene polymer K was obtained by the same charging composition and polymerization method.
  • the physical property values of the first conjugated diene polymer (11) are shown in Table 1.
  • Comparative Example 4 It is a commercially available polybutadiene rubber (manufactured by JSR Corporation, trade name “polybutadiene rubber BR01”). The physical property values are shown in Table 1.
  • GPMOS 3-glycidoxypropyltrimethoxysilane IPOTi; tetraisopropyl titanate EHABi; tris (2-ethylhexanoate) bismuth EHAZrO; bis (2-ethylhexanoate) zirconium oxide EHAAl; tris (2-ethylhexano) Ate) aluminum EHASn; bis (2-ethylhexanoate) tin IPEOS; 3-isocyanatopropyltriethoxysilane STO; sorbitan acid trioleate SML; sorbitan acid monolaurate
  • Example 9 Using the modified conjugated diene polymer A produced in Example 1- (C), a rubber composition (1) was produced according to the formulation shown in Table 2. The resulting rubber composition (1) had a Mooney viscosity (ML 1 + 4 , 100 ° C.) of 51. Further, the obtained rubber composition (1) was vulcanized at 150 ° C. for 12 minutes to prepare a vulcanized rubber. Tensile strength T B of the vulcanized rubber is 20.2 MPa, the index of the low heat build-up (3% tan ⁇ ) is 133, the index of the low temperature properties (-20 °C G ') is 181, the abrasion resistance The index was 124. The index value was calculated based on the vulcanized rubber of Comparative Example 8.
  • Examples 10 to 16 and Comparative Examples 5 to 8 Using the modified conjugated diene polymers B to K or the polymer L produced in Examples 2 to 8 and Comparative Examples 1 to 3, the rubber composition was produced by carrying out the compounding recipe shown in Table 2. The Mooney viscosity was measured for these rubber compositions. Further, the rubber composition was vulcanized at 150 ° C. for 12 minutes to prepare a vulcanized rubber, and the physical property values were evaluated. The results are shown in Table 3.
  • the modified conjugated diene polymer produced by mixing the high molecular weight component (A) and the low molecular weight component (B) and then condensing the first alkoxysilyl group and the second alkoxysilyl group.
  • a rubber composition containing A to H has a low Mooney viscosity at the time of blending and good processability. It can also be seen that the vulcanized rubber is excellent in low heat build-up, low temperature characteristics and wear resistance.
  • the present invention is expected to be used in tire applications such as tire treads, under treads, carcass, sidewalls, and bead parts, as well as anti-vibration rubber, fenders, belts, hoses, and other industrial products. .

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  • Compositions Of Macromolecular Compounds (AREA)
  • Tires In General (AREA)
  • Polymerization Catalysts (AREA)
  • Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)

Abstract

L'invention concerne un procédé de fabrication d'un polymère diène conjugué modifié, ledit procédé comprenant : une étape lors de laquelle un premier groupe alcoxysilyle est introduit dans une terminaison active d'un premier polymère diène conjugué qui contient moins de 10 % de vinyle, qui contient 75 % ou plus d'une liaison 1,4 cis et qui a un poids moléculaire moyen en poids (Mw) de 250 000 à 800 000, pour obtenir un composant (A) ; une étape distincte lors de laquelle un second groupe alcoxysilyle est introduit dans une terminaison active d'un second polymère diène conjugué qui contient moins de 10 % de vinyle, qui contient 75 % ou plus d'une liaison 1,4 cis et qui a un poids moléculaire moyen en poids (Mw) de 10 000 à 150 000, pour obtenir un composant (B) ; et une étape lors de laquelle le composant (A) et le composant (B) sont mélangés, le premier groupe alcoxysilyle et le second groupe alcoxysilyle étant ensuite condensés.
PCT/JP2009/069746 2008-11-25 2009-11-20 Procédé de fabrication d’un polymère diène conjugué modifié, polymère diène conjugué modifié, composition de caoutchouc et pneu Ceased WO2010061802A1 (fr)

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JP2017214534A (ja) * 2016-06-02 2017-12-07 住友ゴム工業株式会社 ゴム組成物およびタイヤ
JP2017214533A (ja) * 2016-06-02 2017-12-07 住友ゴム工業株式会社 ゴム組成物およびタイヤ
WO2017208891A1 (fr) * 2016-06-02 2017-12-07 住友ゴム工業株式会社 Composition de caoutchouc, pneumatique, et procédé de production d'une composition de caoutchouc
JP2017214532A (ja) * 2016-06-02 2017-12-07 住友ゴム工業株式会社 ゴム組成物およびタイヤ
JP2017214535A (ja) * 2016-06-02 2017-12-07 住友ゴム工業株式会社 ゴム組成物の製造方法、ゴム組成物およびタイヤ

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JP5369816B2 (ja) * 2009-03-26 2013-12-18 Ｊｓｒ株式会社 変性共役ジエン系重合体の製造方法、変性共役ジエン系重合体、及びゴム組成物
JP7285940B2 (ja) * 2019-09-20 2023-06-02 株式会社クラレ ゴム組成物、タイヤ用ゴム組成物及び靴底用ゴム組成物
CN115038726B (zh) * 2020-09-25 2024-08-09 株式会社Lg化学 钕催化的共轭二烯类聚合物和包含其的橡胶组合物

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WO2017208891A1 (fr) * 2016-06-02 2017-12-07 住友ゴム工業株式会社 Composition de caoutchouc, pneumatique, et procédé de production d'une composition de caoutchouc
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JP2017214535A (ja) * 2016-06-02 2017-12-07 住友ゴム工業株式会社 ゴム組成物の製造方法、ゴム組成物およびタイヤ

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