WO2018088483A1 - Procédé de production d'un caoutchouc diène conjugué modifié - Google Patents

Procédé de production d'un caoutchouc diène conjugué modifié Download PDF

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Publication number
WO2018088483A1
WO2018088483A1 PCT/JP2017/040454 JP2017040454W WO2018088483A1 WO 2018088483 A1 WO2018088483 A1 WO 2018088483A1 JP 2017040454 W JP2017040454 W JP 2017040454W WO 2018088483 A1 WO2018088483 A1 WO 2018088483A1
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group
conjugated diene
general formula
rubber
integer
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PCT/JP2017/040454
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English (en)
Japanese (ja)
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英順 植田
山岸　英哲
岸本　典久
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日本ゼオン株式会社
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Priority to JP2018550258A priority Critical patent/JP7020423B2/ja
Publication of WO2018088483A1 publication Critical patent/WO2018088483A1/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
    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L15/00—Compositions of rubber derivatives

Definitions

  • the present invention relates to a method for producing a modified conjugated diene rubber, and more particularly to a method for producing a modified conjugated diene rubber capable of giving a rubber cross-linked product excellent in wet grip properties and low heat build-up.
  • the present invention also relates to a modified conjugated diene rubber obtained by this production method, a rubber composition containing the modified conjugated diene rubber, and a crosslinked rubber product thereof.
  • Patent Document 1 a compound having a protected primary amino group and an alkoxysilyl group such as N, N-bis (trimethylsilyl) aminopropylmethyldimethoxysilane is reacted with the active terminal of a conjugated diene polymer. Therefore, attempts have been made to increase the affinity between the conjugated diene polymer and silica.
  • the resulting conjugated diene polymer has a certain degree of affinity for silica, but the dispersibility of silica when blended with silica is not always sufficient, and therefore, the wet grip The improvement effect of heat resistance and low exothermicity was also limited.
  • the present invention has been made in view of such a situation, and provides a method for producing a modified conjugated diene rubber that can give a crosslinked rubber excellent in wet grip and low heat build-up. With the goal.
  • the present inventors have conducted extensive studies on a modifier for modifying the active terminal of a conjugated diene polymer.
  • the modifier has a cyclic siloxane structure and is protected.
  • Modified conjugated diene rubber obtained by using a specific silane compound with an amino group-containing organic group and reacting this with the active end of a conjugated diene polymer having an active end is good for fillers such as silica. It was found that a rubber cross-linked product excellent in wet grip properties and low heat build-up properties can be obtained, and the present invention has been completed.
  • a conjugated diene polymer having an active terminal is obtained by polymerizing a monomer comprising at least a conjugated diene compound using an organic active metal compound as a polymerization initiator in an inert solvent. And a second step of reacting a compound represented by the following general formula (1) with the active terminal of the conjugated diene polymer having the active terminal: A method is provided.
  • R 1 and R 3 are each independently a monovalent hydrocarbon group, a hydrogen atom or a hydroxyl group, and R 2 is an arbitrary organic group, a hydrogen atom or a hydroxyl group, X 1 is a protected amino group-containing organic group containing a primary amino group protected by a protecting group, m is an integer of 1 to 30, n is an integer of 0 to 29, and m + n is 3 to 30 is there.)
  • the compound represented by the general formula (1) is preferably a compound represented by the following general formula (2).
  • R 1 , R 4 to R 6 are each independently a monovalent hydrocarbon group, a hydrogen atom or a hydroxyl group, and X 1 is a primary group protected by a protecting group.
  • X 2 is an alkoxy group-containing organic group or an epoxy group-containing organic group
  • m is an integer of 1 to 29
  • p is an integer of 1 to 29
  • q is 0
  • the content ratio of the protected amino group-containing organic group to the alkoxy group-containing organic group and / or the epoxy group-containing organic group is expressed as “protected amino group-containing organic group /
  • the molar ratio of “alkoxy group-containing organic group and / or epoxy group-containing organic group” is preferably 0.1 to 10.
  • the compound represented by the general formula (1) is represented by the following general formula (3), the following general formula (4), or the following general formula (5) as the protected amino group-containing organic group. It is preferable that it contains a group.
  • R 7 to R 10 are each independently an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms, and e is an integer of 1 to 12) F is an integer from 1 to 12.
  • R 11 to R 16 are each independently an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms, and g is an integer of 1 to 12) .
  • R 17 and R 18 are each independently an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms, and h is an integer of 1 to 12) .
  • the amount of the compound represented by the general formula (1) is preferably 0.01 to 30 moles relative to 1 mole of the organic active metal as a polymerization initiator, More preferably, it is ⁇ 5 mol.
  • the present invention also provides a modified conjugated diene rubber obtained by any one of the above production methods. Furthermore, according to the present invention, there is provided a rubber composition comprising 10 to 200 parts by weight of silica with respect to 100 parts by weight of a rubber component containing the modified conjugated diene rubber.
  • the rubber composition of the present invention preferably contains a crosslinking agent.
  • a rubber cross-linked product obtained by cross-linking the rubber composition, and a tire comprising the rubber cross-linked product.
  • a modified conjugated diene rubber capable of giving a rubber cross-linked product excellent in wet grip properties and low heat build-up properties
  • a rubber composition containing the modified conjugated diene rubber, and the rubber composition are cross-linked. It is possible to provide a rubber cross-linked product excellent in wet grip and low heat build-up, and a tire comprising the rubber cross-linked product.
  • the method for producing a modified conjugated diene rubber according to the present invention has an active terminal by polymerizing a monomer containing at least a conjugated diene compound using an organic active metal compound as a polymerization initiator in an inert solvent.
  • a monomer comprising at least a conjugated diene compound is polymerized in an inert solvent using an organic active metal compound as a polymerization initiator, and a conjugated diene having an active terminal is obtained. This is a step of obtaining a polymer.
  • the conjugated diene compound used for polymerization in order to obtain a conjugated diene polymer having an active terminal is not particularly limited, and for example, 1,3-butadiene, isoprene, 2,3-dimethyl-1 , 3-butadiene, 1,3-pentadiene, 2-methyl-3-ethyl-1,3-butadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene, 1,3-cyclohexadiene, etc. Can be mentioned. Of these, 1,3-butadiene, isoprene and 1,3-pentadiene are preferred, and 1,3-butadiene and isoprene are particularly preferred. In addition, these conjugated diene compounds may be used individually by 1 type, and may be used in combination of 2 or more type.
  • the conjugated diene polymer having an active end produced in the first step may be obtained by copolymerizing an aromatic vinyl compound in addition to the conjugated diene compound.
  • the aromatic vinyl compound is not particularly limited, and for example, styrene, ⁇ -methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2-ethylstyrene, 3-ethylstyrene, 4-ethylstyrene 2,4-diisopropylstyrene, 2,4-dimethylstyrene, 4-t-butylstyrene, 5-t-butyl-2-methylstyrene, vinylnaphthalene, dimethylaminomethylstyrene, dimethylaminoethylstyrene, etc.
  • the conjugated diene polymer having an active end produced in the first step preferably contains 50 to 100% by weight of a conjugated diene monomer unit, particularly preferably contains 55 to 100% by weight, Those containing 0 to 50% by weight of the vinyl group monomer group are preferred, and those containing 0 to 45% by weight are particularly preferred.
  • the conjugated diene polymer having an active end is optionally added to the conjugated diene compound as well as other units other than the aromatic vinyl compound as long as the object of the present invention is not impaired. It may be formed by copolymerizing a monomer containing a monomer.
  • Examples of other monomers include ⁇ , ⁇ -unsaturated nitriles such as acrylonitrile and methacrylonitrile; unsaturated carboxylic acids or acid anhydrides such as acrylic acid, methacrylic acid, and maleic anhydride; methyl methacrylate, acrylic Unsaturated carboxylic acid esters such as ethyl acrylate and butyl acrylate; Non-conjugated dienes such as 1,5-hexadiene, 1,6-heptadiene, 1,7-octadiene, dicyclopentadiene, 5-ethylidene-2-norbornene; etc. Can be mentioned. These monomers are preferably 10% by weight or less, more preferably 5% by weight or less as monomer units in the conjugated diene polymer having an active terminal.
  • the inert solvent used in the first step of the production method of the present invention is not particularly limited as long as it is usually used in solution polymerization and does not inhibit the polymerization reaction.
  • Specific examples of the inert solvent include chain aliphatic hydrocarbons such as butane, pentane, hexane, heptane, 2-butene; alicyclic hydrocarbons such as cyclopentane, cyclohexane, cyclohexene; benzene, toluene, xylene, etc. Aromatic hydrocarbons; and the like.
  • These inert solvents may be used individually by 1 type, and may be used in combination of 2 or more type.
  • the amount of the inert solvent used is such that the monomer concentration is, for example, 1 to 50% by weight, preferably 10 to 40% by weight.
  • the organic active metal compound used as a polymerization initiator is not particularly limited as long as it can polymerize a monomer containing a conjugated diene compound to give a conjugated diene polymer having an active terminal,
  • a polymerization initiator mainly comprising an organic alkali metal compound, an organic alkaline earth metal compound, a lanthanum series metal compound, or the like is preferably used.
  • organic alkali metal compound examples include organic monolithium compounds such as n-butyllithium, sec-butyllithium, t-butyllithium, hexyllithium, phenyllithium and stilbenelithium; dilithiomethane, 1,4-dilithiobutane, 1,4 -Organic polyvalent lithium compounds such as dilithio-2-ethylcyclohexane, 1,3,5-trilithiobenzene, 1,3,5-tris (lithiomethyl) benzene; organic sodium compounds such as sodium naphthalene; organic such as potassium naphthalene Potassium compounds; and the like.
  • organic monolithium compounds such as n-butyllithium, sec-butyllithium, t-butyllithium, hexyllithium, phenyllithium and stilbenelithium
  • dilithiomethane 1,4-dilithiobutane
  • organic alkaline earth metal compound examples include di-n-butylmagnesium, di-n-hexylmagnesium, diethoxycalcium, calcium distearate, di-t-butoxystrontium, diethoxybarium, and diisopropoxybarium. Diethyl mercaptobarium, di-t-butoxybarium, diphenoxybarium, diethylaminobarium, barium distearate, diketylbarium and the like.
  • a polymerization initiator having a lanthanum series metal compound as a main catalyst for example, a lanthanum series metal comprising a lanthanum series metal such as lanthanum, cerium, praseodymium, neodymium, samarium, gadolinium, a carboxylic acid, and a phosphorus-containing organic acid And a polymerization initiator composed of this salt and a cocatalyst such as an alkylaluminum compound, an organoaluminum hydride compound, and an organoaluminum halide compound.
  • a lanthanum series metal comprising a lanthanum series metal such as lanthanum, cerium, praseodymium, neodymium, samarium, gadolinium, a carboxylic acid, and a phosphorus-containing organic acid
  • a polymerization initiator composed of this salt and a cocatalyst such as an alkylalumin
  • an organic monolithium compound and an organic polyvalent lithium compound are preferable, an organic monolithium compound is more preferable, and n-butyllithium is particularly preferable.
  • the organic alkali metal compound is used as an organic alkali metal amide compound by previously reacting with a secondary amine such as dibutylamine, dihexylamine, dibenzylamine, pyrrolidine, hexamethyleneimine, and heptamethyleneimine. Also good.
  • These polymerization initiators may be used individually by 1 type, and may be used in combination of 2 or more type.
  • the amount of the organic active metal compound used as the polymerization initiator may be determined according to the molecular weight of the target polymer, but is usually 1 to 50 mmol, preferably 1.5 to 20 per 1000 g of monomer. In the range of millimolar, more preferably 2-15 millimolar.
  • the polymerization temperature in the first step of the production method of the present invention is usually in the range of ⁇ 80 to + 150 ° C., preferably 0 to 100 ° C., more preferably 30 to 90 ° C.
  • any of batch type and continuous type can be adopted.
  • a conjugated diene monomer unit and an aromatic vinyl monomer are used.
  • the batch method is preferred because it is easy to control the randomness of the bond with the unit.
  • the conjugated diene polymer having an active terminal is composed of two or more types of monomer units
  • various bonding modes such as a block shape, a taper shape, and a random shape.
  • a random binding mode is preferred. By making it random, the resulting rubber cross-linked product is excellent in low heat build-up.
  • a polar compound is added to the inert organic solvent during the polymerization. It is preferable to do.
  • the polar compound include ether compounds such as dibutyl ether, tetrahydrofuran and 2,2-di (tetrahydrofuryl) propane; tertiary amines such as tetramethylethylenediamine; alkali metal alkoxides; phosphine compounds.
  • ether compounds and tertiary amines are preferable, tertiary amines are more preferable, and tetramethylethylenediamine is particularly preferable.
  • These polar compounds may be used individually by 1 type, and may be used in combination of 2 or more type.
  • the amount of the polar compound used may be determined according to the target vinyl bond content, and is preferably 0.001 to 100 mol, more preferably 0, relative to 1 mol of the organic active metal compound used as the polymerization initiator. .01 to 10 moles. When the amount of the polar compound used is within this range, it is easy to adjust the vinyl bond content in the conjugated diene monomer unit, and problems due to deactivation of the polymerization initiator hardly occur.
  • a conjugated diene polymer having an active terminal can be obtained by polymerizing a monomer containing a conjugated diene compound.
  • the vinyl bond content in the conjugated diene monomer unit in the conjugated diene polymer having an active end obtained in the first step of the production method of the present invention is preferably 1 to 90 mol%, more preferably 5 ⁇ 85 mol%.
  • the vinyl bond amount is in the above range, the resulting rubber cross-linked product has excellent low heat build-up.
  • the peak top molecular weight detected by gel permeation chromatography (hereinafter also referred to as GPC) of the conjugated diene polymer having an active terminal obtained in the first step of the production method of the present invention is 10 in terms of polystyrene. It is preferably from 1,000,000 to 1,000,000, more preferably from 50,000 to 850,000, and particularly preferably from 100,000 to 700,000. When a plurality of peaks of the conjugated diene polymer are observed, the peak top molecular weight of the peak having the smallest molecular weight derived from the conjugated diene polymer detected by GPC is used as the conjugated diene polymer having an active end.
  • the peak top molecular weight of When the peak top molecular weight of the conjugated diene polymer having an active end is in the above range, the resulting rubber cross-linked product is excellent in low heat build-up.
  • the molecular weight distribution represented by the ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the conjugated diene polymer having an active end obtained in the first step of the production method of the present invention is: Preferably it is 1.0 to 1.5, more preferably 1.0 to 1.4, and particularly preferably 1.0 to 1.3.
  • this molecular weight distribution value (Mw / Mn) is in the above range, the resulting rubber cross-linked product is excellent in low heat build-up.
  • R 1 and R 3 are each independently a monovalent hydrocarbon group, a hydrogen atom or a hydroxyl group, and R 2 is an arbitrary organic group, a hydrogen atom or a hydroxyl group, X 1 is a protected amino group-containing organic group containing a primary amino group protected by a protecting group, m is an integer of 1 to 30, n is an integer of 0 to 29, and m + n is 3 to 30 is there.)
  • the conjugated diene is reacted by reacting the compound represented by the general formula (1) with the active terminus of the conjugated diene polymer having an active terminus obtained in the first step.
  • System rubber can be modified to improve the affinity for silica and other fillers, and when silica and other fillers are blended, the dispersibility of silica and other fillers can be increased.
  • a rubber cross-linked product having wet grip properties.
  • m is an integer of 1 to 30, preferably an integer of 1 to 20, more preferably an integer of 1 to 10.
  • n is an integer of 0 to 29, preferably an integer of 0 to 20, and more preferably an integer of 0 to 10.
  • M + n is 3 to 30, preferably 3 to 20, and more preferably 3 to 10.
  • X 1 is a protected amino group-containing organic group containing a primary amino group protected by a protecting group (hereinafter, also simply referred to as “protected amino group-containing organic group”).
  • the protected amino group-containing organic group is not particularly limited as long as it has a structure in which a protective group is introduced into the amino group, and the two hydrogen atoms of the primary amino group (ie, —NH 2 ) It is preferably a group containing a protected amino group having a structure substituted with a group acting as a protecting group.
  • a protecting group is not particularly limited, but is preferably one capable of introducing an inactive structure with respect to the active end of the conjugated diene polymer having an active end obtained in the first step.
  • Examples of such a protecting group include a hydrocarbyl group or a silyl group, and a silyl group is preferable.
  • a protecting group in addition to being capable of introducing an inactive structure to the active end of the conjugated diene polymer having an active end obtained in the first step, an acid or a base is used. More preferably, it can be deprotected by a method or a hydrolysis reaction.
  • the protecting group is deprotectable, the protected amino group-containing organic group contains a primary amino group or a secondary amino group by deprotecting the protecting group.
  • the affinity with fillers such as silica can be further increased.
  • Suitable examples of such a protected amino group-containing organic group include groups represented by the following general formula (3), the following general formula (4), or the following general formula (5).
  • R 7 to R 10 are each independently an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms.
  • E is an integer of 1 to 12, preferably an integer of 1 to 6, more preferably an integer of 1 to 4.
  • R 11 to R 16 are each independently an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms.
  • G is an integer of 1 to 12, preferably an integer of 1 to 6, more preferably an integer of 1 to 4.
  • R 17 and R 18 are each independently an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms.
  • H is an integer of 1 to 12, preferably an integer of 1 to 6, more preferably an integer of 1 to 4.
  • a group represented by —SiR 7 R 8 — (CH 2 ) f —SiR 9 R 10 — acts as a protecting group.
  • a group represented by —SiR 11 R 12 R 13 and a group represented by —SiR 14 R 15 R 16 act as a protecting group.
  • the group represented by R 17 and the group represented by R 18 act as protective groups.
  • those having a silyl group as the protecting group are preferable from the viewpoint that they function well as a protecting group and can also perform a deprotection reaction well, and are represented by the above formula (3).
  • the group and the group represented by the above formula (4) are preferable.
  • the protected amino group constituting the protected amino group-containing organic group include bis (trimethylsilyl) amino group, bis (triethylsilyl) amino group, bis (triisopropylsilyl) amino group, and bis (triphenylsilyl) amino group.
  • R 1 and R 3 are each independently a monovalent hydrocarbon group, a hydrogen atom or a hydroxyl group, preferably a monovalent hydrocarbon group.
  • the monovalent hydrocarbon group is preferably an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, and further preferably a methyl group.
  • R 2 is an arbitrary organic group, a hydrogen atom or a hydroxyl group, and examples of the arbitrary organic group include an alkoxy group-containing organic group, an epoxy group-containing organic group, and a monovalent hydrocarbon group.
  • n is 2 or more, but so that the R 2 there are a plurality, the plurality of R 2 may be different and the same as each other.
  • the modification effect of the conjugated diene rubber specifically, the affinity for the filler such as silica is improved, and the filler such as silica is blended.
  • the effect of enhancing the dispersibility of fillers such as silica is high, and thereby, the resulting rubber cross-linked product can be made more excellent in low exothermic property and wet grip property, from the following general formula
  • the compound represented by (2) is preferred.
  • R 1 , R 4 to R 6 are each independently a monovalent hydrocarbon group, a hydrogen atom or a hydroxyl group, and X 1 is a primary group protected by a protecting group.
  • a protected amino group-containing organic group containing an amino group, X 2 is an alkoxy group-containing organic group or an epoxy group-containing organic group, m is an integer of 1 to 29, p is an integer of 1 to 29, and q is 0 (It is an integer of ⁇ 28, and m + p + q is 3 to 30.)
  • m is an integer of 1 to 29, preferably an integer of 1 to 20, and more preferably an integer of 1 to 10.
  • p is an integer of 1 to 29, preferably an integer of 1 to 20, more preferably an integer of 1 to 10
  • q is an integer of 0 to 28, preferably an integer of 0 to 20, more preferably It is an integer of 0 to 10, particularly preferably 0.
  • m + p + q is 3 to 30, preferably 3 to 20, and more preferably 3 to 10.
  • X 1 is the same as the above general formula (1), and the preferred embodiment is also the same as the above general formula (1).
  • X 2 is an alkoxy group-containing organic group or an epoxy group-containing organic group is preferably an alkoxy group-containing organic group.
  • p is 2 or more, but so that the X 2 there are a plurality, the plurality of X 2 may be different and the same as each other.
  • the alkoxy group-containing organic group may be any group that contains an alkoxy group, and is not particularly limited.
  • the alkoxy group include alkoxy groups such as a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, and a butoxy group,
  • Examples include alkoxysilyl groups, but it is possible to improve the coupling ratio of two or more branches in the resulting modified conjugated diene rubber, thereby further improving wet grip and low heat build-up. From the standpoint, those containing an alkoxysilyl group are preferred.
  • an alkoxy group-containing organic group usually acts as a binding site that binds to a conjugated diene polymer having an active end.
  • the alkoxysilyl group-containing organic group is not particularly limited as long as it is a group containing an alkoxysilyl group, and the alkoxysilyl group contains any of a monoalkoxysilyl group, a dialkoxysilyl group, or a trialkoxysilyl group.
  • a group represented by the following general formula (6) may be mentioned.
  • R 19 each independently represents an alkyl group having 1 to 20 carbon atoms, preferably an alkyl group having 1 to 10 carbon atoms, and R 20 represents a hydrogen atom or a carbon number.
  • j is an integer of 1 to 20, preferably an integer of 2 to 15, more preferably an integer of 3 to 10
  • k is an integer of 1 to 3.
  • R 19 is a presence of a plurality
  • the plurality of R 19 may be different be the same as each other.
  • R 20 is a presence of a plurality
  • the plurality of R 20 may be different be the same as each other.
  • alkoxysilyl group contained in the alkoxysilyl group-containing organic group include a trialkoxysilyl group such as a trimethoxysilyl group and a triethoxysilyl group; a dimethoxymethylsilyl group, a diethoxymethylsilyl group, a dimethoxyethylsilyl group, Dialkoxyalkylsilyl groups such as diethoxyethylsilyl group; monoalkoxydialkyl groups such as methoxydimethylsilyl group, ethoxydimethylsilyl group, methoxydiethylsilyl group, ethoxydiethylsilyl group; and the like.
  • the polymer modifier when used as a polymer modifier, for example, when used as a polymer modifier, it is possible to increase the affinity between the polymer and a filler such as silica.
  • the trialkoxysilyl group is preferable and the trimethoxysilyl group is more preferable from the viewpoint that the effect of improving the resistance is high.
  • the epoxy group-containing organic group is not particularly limited as long as it is an organic group containing an epoxy group, but is not limited to 2-glycidoxyethyl group, 3-glycidoxypropyl group, 4-glycidoxybutyl group.
  • a glycidoxyalkyl group such as 2- (3,4-epoxycyclohexyl) ethyl group, 3- (3,4-epoxycyclohexyl) propyl group, 2- (3,4-epoxynorbornyl) ethyl group, 2 -Epoxycycloalkylalkyl groups such as (3,4-epoxy-3-methylcyclohexyl) -2-methylethyl group; oxiranylalkyl groups such as 4-oxiranylbutyl group and 8-oxiranyloctyl group; Etc.
  • a glycidoxyalkyl group is preferable, and a 3-glycidoxypropyl group is particularly preferable.
  • R 1 and R 4 to R 6 are each independently a monovalent hydrocarbon group, a hydrogen atom or a hydroxyl group, preferably a monovalent hydrocarbon group.
  • the monovalent hydrocarbon group is preferably an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, and further preferably a methyl group. It is.
  • the content ratio of the protected amino group-containing organic group and the alkoxy group-containing organic group and / or the epoxy group-containing organic group is not particularly limited.
  • the molar ratio of “group-containing organic group / (alkoxy group-containing organic group and / or epoxy group-containing organic group)” is preferably 0.1 to 10.0, more preferably 0.2 to 5.0, Preferably it is 0.25 to 4.0, and particularly preferably 0.5 to 1.5.
  • the usage-amount of the compound represented by the said General formula (1) in a 2nd process is the organic active metal compound as a polymerization initiator used in the 1st process mentioned above.
  • the ratio is preferably 0.01 to 30 moles, more preferably 0.05 to 5 moles, and further preferably 0.1 to 3 moles per mole of metal atoms. preferable.
  • a cyclic main chain structure composed of repeating units represented by —Si—O— as shown in the general formula (1) is used as a modifier used when producing a modified conjugated diene rubber.
  • the compound which has is used.
  • the effect of introducing a modified structure introduced by a modifier, ie, the above-described effect The effect of the protected amino group-containing organic group can be made sufficient.
  • the effect of improving the affinity for fillers such as silica can be made more satisfactory, and as a result, the obtained rubber cross-linked product is excellent in wet grip and low heat build-up. Is something that can be done.
  • the second step of the production method of the present invention as a method of reacting the compound represented by the general formula (1) with the active end of the conjugated diene polymer having the active end obtained in the first step described above.
  • the conjugated diene polymer having an active end obtained in the first step described above and the compound represented by the general formula (1) in a solvent capable of dissolving them The method of mixing etc. is mentioned.
  • the solvent used at this time those exemplified as the solvent used for the polymerization of the conjugated diene polymer described above can be used.
  • the conjugated diene polymer having an active end obtained in the first step described above is kept in the polymerization solution used for the polymerization, and is represented by the general formula (1).
  • the method of adding the compound is simple and preferred.
  • the compound represented by the general formula (1) is preferably dissolved in the inert solvent used for the polymerization and added to the polymerization system, and the solution concentration is 1 to 50. It is preferable to set it as the range of weight%.
  • the reaction temperature in the second step is not particularly limited, but is usually 0 to 120 ° C.
  • the reaction time is not particularly limited, but is usually 1 minute to 1 hour.
  • the timing of adding the compound represented by the general formula (1) to the solution containing the conjugated diene polymer having an active terminal is not particularly limited, but the polymerization reaction is not completed and the conjugate having an active terminal is present.
  • the state in which the solution containing the diene polymer also contains a monomer, more specifically, the solution containing the conjugated diene polymer having an active terminal is 100 ppm or more, more preferably 300 to 50. It is desirable to add the compound represented by the general formula (1) to this solution in a state containing 1,000 ppm of monomer.
  • the active end of the conjugated diene polymer is not limited so long as the effect of the present invention is not inhibited.
  • the part may be inactivated by adding a coupling agent, a modifier and the like conventionally used in the polymerization system.
  • An anti-aging agent such as a phenol-based stabilizer, a phosphorus-based stabilizer, or a sulfur-based stabilizer may be added to the modified conjugated diene rubber solution obtained as described above, if desired. What is necessary is just to determine suitably the addition amount of an anti-aging agent according to the kind etc.
  • an extension oil may be blended to form an oil-extended rubber.
  • the extender oil include paraffinic, aromatic and naphthenic petroleum softeners, plant softeners, and fatty acids.
  • the content of polycyclic aromatics extracted by the method of IP346 the inspection method of THE INSTITUTE PETROLEUM in the UK
  • the amount used is usually 5 to 100 parts by weight with respect to 100 parts by weight of the modified conjugated diene rubber.
  • the modified conjugated diene rubber after the modification reaction thus obtained is separated from the reaction mixture by removing the solvent by steam stripping to obtain a solid modified conjugated diene rubber.
  • the protected amino group-containing organic compound derived from the compound represented by the above general formula (1) introduced into the modified conjugated diene rubber after the modification reaction as described above by steam stripping. It is considered that a primary amino group or a secondary amino group is generated by deprotecting the protecting group in the group by hydrolysis.
  • the modified conjugated diene rubber obtained by the production method of the present invention contains the compound represented by the general formula (1) or a structure forming a coupling structure having two or more branches via a coupling agent.
  • the modified conjugated diene rubber preferably has a content ratio (coupling ratio) of the structure forming a coupling structure having two or more branches of the compound represented by the general formula (1). Is 5% by weight or more, more preferably 8% by weight or more, and still more preferably 10% by weight or more.
  • the content ratio of the structure forming a coupling structure having two or more branches is in the above-mentioned range, the effect of improving wet grip properties and low heat build-up becomes more remarkable, which is preferable.
  • the weight average molecular weight (Mw) of the modified conjugated diene rubber obtained by the production method of the present invention is not particularly limited, but is usually 1,000 to 3,000 as a value measured by gel permeation chromatography in terms of polystyrene. 1,000, preferably 10,000 to 2,000,000, more preferably 100,000 to 1,500,000.
  • Mw weight average molecular weight
  • the molecular weight distribution represented by the ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the modified conjugated diene rubber obtained by the production method of the present invention is not particularly limited. Is 1.0 to 5.0, particularly preferably 1.0 to 3.0. By setting the molecular weight distribution of the modified conjugated diene rubber within the above range, the resulting rubber cross-linked product becomes more excellent due to low heat build-up.
  • the Mooney viscosity (ML 1 + 4, 100 ° C.) of the modified conjugated diene rubber obtained by the production method of the present invention is also not particularly limited, but is usually in the range of 20 to 200, preferably 30 to 150. By setting the Mooney viscosity of the modified conjugated diene rubber to the above range, the processability of the rubber composition becomes excellent.
  • the modified conjugated diene rubber is an oil-extended rubber
  • the Mooney viscosity of the oil-extended rubber is preferably in the above range.
  • the modified conjugated diene rubber thus obtained can be suitably used for various applications after adding compounding agents such as a filler and a crosslinking agent.
  • compounding agents such as a filler and a crosslinking agent.
  • silica is blended as a filler
  • a rubber composition suitably used for obtaining a crosslinked rubber product having excellent wet grip properties and low heat build-up properties is provided.
  • the rubber composition of the present invention is a composition comprising 10 to 200 parts by weight of silica with respect to 100 parts by weight of a rubber component containing the modified conjugated diene rubber obtained by the production method of the present invention described above.
  • silica used in the present invention examples include dry method white carbon, wet method white carbon, colloidal silica, and precipitated silica.
  • wet method white carbon mainly containing hydrous silicic acid is preferable.
  • a carbon-silica dual phase filler in which silica is supported on the carbon black surface may be used.
  • These silicas can be used alone or in combination of two or more.
  • nitrogen adsorption specific surface area of silica used is preferably 50 ⁇ 300m 2 / g, more preferably 80 ⁇ 220m 2 / g, particularly preferably 100 ⁇ 170m 2 / g.
  • the pH of silica is preferably 5-10.
  • the compounding amount of silica in the rubber composition of the present invention is 10 to 200 parts by weight, preferably 30 to 150 parts by weight, more preferably 50 to 100 parts by weight with respect to 100 parts by weight of the rubber component in the rubber composition. Part.
  • the rubber composition of the present invention may further contain a silane coupling agent from the viewpoint of further improving the low heat build-up.
  • a silane coupling agent examples include vinyltriethoxysilane, ⁇ - (3,4-epoxycyclohexyl) ethyltrimethoxysilane, N- ( ⁇ -aminoethyl) - ⁇ -aminopropyltrimethoxysilane, 3-octathio- 1-propyl-triethoxysilane, bis (3- (triethoxysilyl) propyl) disulfide, bis (3- (triethoxysilyl) prol) tetrasulfide, ⁇ -trimethoxysilylpropyldimethylthiocarbamyl tetrasulfide, and ⁇ -Trimethoxysilylpropylbenzothiazyl tetrasulfide and the like.
  • These silane coupling agents can be used alone or
  • the rubber composition of the present invention may further contain carbon black such as furnace black, acetylene black, thermal black, channel black, and graphite. Among these, furnace black is preferable. These carbon blacks can be used alone or in combination of two or more.
  • the compounding amount of carbon black is usually 120 parts by weight or less with respect to 100 parts by weight of the rubber component in the rubber composition.
  • the method of adding silica to the rubber component containing the modified conjugated diene rubber of the present invention is not particularly limited, and a method of adding and kneading a solid rubber component (dry kneading method) or a modified conjugated diene A method (wet kneading method) that is added to a solution containing a rubber and solidified and dried can be applied.
  • the rubber composition of the present invention preferably further contains a cross-linking agent.
  • the crosslinking agent include sulfur-containing compounds such as sulfur and sulfur halides, organic peroxides, quinonedioximes, organic polyvalent amine compounds, and alkylphenol resins having a methylol group. Among these, sulfur is preferably used.
  • the amount of the crosslinking agent is preferably 0.1 to 15 parts by weight, more preferably 0.5 to 5 parts by weight, and particularly preferably 1 to 4 parts by weight with respect to 100 parts by weight of the rubber component in the rubber composition. It is.
  • the rubber composition of the present invention includes a crosslinking accelerator, a crosslinking activator, an anti-aging agent, a filler (excluding silica and carbon black), an activator, and a process oil in accordance with conventional methods.
  • a crosslinking accelerator excluding silica and carbon black
  • a filler excluding silica and carbon black
  • an activator excluding silica and carbon black
  • a process oil in accordance with conventional methods.
  • Plasticizers, lubricants, tackifiers and the like can be blended in the required amounts.
  • crosslinking accelerator When sulfur or a sulfur-containing compound is used as the crosslinking agent, it is preferable to use a crosslinking accelerator and a crosslinking activator in combination.
  • the crosslinking accelerator include sulfenamide-based crosslinking accelerators; guanidine-based crosslinking accelerators; thiourea-based crosslinking accelerators; thiazole-based crosslinking accelerators; thiuram-based crosslinking accelerators; dithiocarbamic acid-based crosslinking accelerators; A crosslinking accelerator; and the like. Among these, those containing a sulfenamide-based crosslinking accelerator are preferable. These crosslinking accelerators are used alone or in combination of two or more.
  • the amount of the crosslinking accelerator is preferably 0.1 to 15 parts by weight, more preferably 0.5 to 5 parts by weight, and particularly preferably 1 to 4 parts by weight with respect to 100 parts by weight of the rubber component in the rubber composition. Part.
  • crosslinking activator examples include higher fatty acids such as stearic acid; zinc oxide. These crosslinking activators are used alone or in combination of two or more.
  • the amount of the crosslinking activator is preferably 0.05 to 20 parts by weight, particularly preferably 0.5 to 15 parts by weight based on 100 parts by weight of the rubber component in the rubber composition.
  • the rubber composition of the present invention may be blended with other rubber other than the modified conjugated diene rubber obtained by the production method of the present invention described above.
  • other rubbers include natural rubber, polyisoprene rubber, emulsion polymerization styrene-butadiene copolymer rubber, solution polymerization styrene-butadiene copolymer rubber, and polybutadiene rubber (high cis-BR and low cis BR).
  • polybutadiene rubber containing crystal fibers made of 1,2-polybutadiene polymer.
  • Styrene-isoprene copolymer rubber butadiene-isoprene copolymer rubber, styrene-isoprene-butadiene copolymer rubber, acrylonitrile- Of butadiene copolymer rubber, acrylonitrile-styrene-butadiene copolymer rubber, etc., those other than the above-mentioned modified conjugated diene rubber.
  • natural rubber, polyisoprene rubber, polybutadiene rubber, and solution-polymerized styrene-butadiene copolymer rubber are preferable. These rubbers can be used alone or in combination of two or more.
  • the modified conjugated diene rubber obtained by the production method of the present invention preferably occupies 10 to 100% by weight of the rubber component in the rubber composition, and occupies 50 to 100% by weight. Is particularly preferred.
  • the modified conjugated diene rubber obtained by the production method of the present invention in the rubber component at such a ratio, it is possible to obtain a crosslinked rubber product having low heat build-up and excellent wet grip properties.
  • each component may be kneaded according to a conventional method.
  • a component excluding a thermally unstable component such as a crosslinking agent or a crosslinking accelerator and a modified conjugated diene rubber are used.
  • a heat-unstable component such as a crosslinking agent or a crosslinking accelerator can be mixed with the kneaded product to obtain a desired composition.
  • the kneading temperature of the component excluding the thermally unstable component and the modified conjugated diene rubber is preferably 80 to 200 ° C., more preferably 120 to 180 ° C., and the kneading time is preferably 30 seconds to 30 minutes. It is.
  • the kneaded product and the thermally unstable component are usually mixed after cooling to 100 ° C. or lower, preferably 80 ° C. or lower.
  • the rubber cross-linked product of the present invention is obtained by cross-linking the rubber composition of the present invention described above.
  • the rubber cross-linked product of the present invention uses the rubber composition of the present invention, for example, is molded by a molding machine corresponding to a desired shape, for example, an extruder, an injection molding machine, a compressor, a roll, and heated. Can be produced by carrying out a crosslinking reaction and fixing the shape as a crosslinked product.
  • crosslinking may be performed after molding in advance, or crosslinking may be performed simultaneously with molding.
  • the molding temperature is usually 10 to 200 ° C, preferably 25 to 120 ° C.
  • the crosslinking temperature is usually 100 to 200 ° C., preferably 130 to 190 ° C.
  • the crosslinking time is usually 1 minute to 24 hours, preferably 2 minutes to 12 hours, particularly preferably 3 minutes to 6 hours. .
  • a heating method a general method used for crosslinking of rubber such as press heating, steam heating, oven heating, hot air heating, etc. may be appropriately selected.
  • the rubber cross-linked product of the present invention thus obtained is obtained by using the modified conjugated diene rubber obtained by the above-described production method of the present invention, and therefore has excellent wet grip properties and low heat build-up properties. It is.
  • the modified conjugated diene rubber obtained by the production method of the present invention is obtained by using the compound represented by the above general formula (1) as a modifier. In addition, it has a high affinity for fillers such as silica, and it can disperse fillers such as silica well. Therefore, the rubber cross-linked product of the present invention obtained by using the modified conjugated diene rubber obtained by the production method of the present invention has excellent wet grip properties and low heat build-up properties.
  • the rubber cross-linked product of the present invention makes use of such characteristics, and for example, in tires, materials for tire parts such as cap treads, base treads, carcass, sidewalls and bead parts; hoses, belts, mats, It can be used in various applications such as vibration rubber and other various industrial article materials; resin impact resistance improvers; resin film buffers; shoe soles; rubber shoes; golf balls;
  • the rubber cross-linked product of the present invention is excellent in wet grip properties and low heat build-up properties, it can be suitably used as a tire material, particularly a low fuel consumption tire material, and is optimal for tread applications.
  • the molecular weight of the rubber was determined as a molecular weight in terms of polystyrene by gel permeation chromatography. Specific measurement conditions were as follows. Measuring instrument: High-performance liquid chromatograph (trade name “HLC-8220” manufactured by Tosoh Corporation) Column: manufactured by Tosoh Corporation, two product names “GMH-HR-H” were connected in series.
  • Detector differential refractometer (trade name “RI-8220” manufactured by Tosoh Corporation) Eluent: Tetrahydrofuran Column temperature: 40 ° C
  • the area ratio of the peak portion having a peak top molecular weight of 1.9 times or more of the peak top molecular weight indicated by the peak derived from the polymer having the smallest molecular weight relative to the total elution area is obtained from the obtained chart.
  • the coupling rate of the branched conjugated diene rubber was 2 or more branches (content ratio of 2 or more branched structures).
  • Example 1 [Production of denaturant 1] The reactor was charged with 31.8 g of methylhydrogencyclosiloxane represented by the following formula (7) and heated to 40 ° C. with stirring under a nitrogen stream. Next, 1.3 g of a toluene solution of platinum-1,3-divinyl-1,3-dimethyldisiloxane complex (Pt concentration 0.17 wt%) was added, and 1-allyl-2,2 ′, 5,5′- 52.8 g of tetramethyl- (1-aza-2,5-disilacyclopentane) was added dropwise so as to keep the reaction temperature at 40 to 75 ° C. After completion of the dropping, stirring was continued at 70 to 75 ° C.
  • Pt concentration 0.17 wt% platinum-1,3-divinyl-1,3-dimethyldisiloxane complex
  • reaction solution 0.5 g was sampled and it was confirmed that the reaction was completed by an alkali decomposition gas generation method.
  • the reaction solution was heated to 155 ° C. under reduced pressure to distill off the low boiling point for 3 hours, and 134.3 g of the modifier 1 represented by the following formula (8) was obtained.
  • the structure represented by the following formula (8) was also confirmed by 1 H-NMR.
  • the viscosity of the obtained modifier 1 was 230 mm 2 / s as measured according to JIS-Z-8803 at 25 ° C. using an Ubbelohde viscosity tube.
  • the polymerization reaction was continued for 60 minutes, and after confirming that the polymerization conversion rate was in the range of 95% to 100%, the modifier 1 obtained above (compound represented by the above formula (8)) 1.35 parts (1.50 moles relative to the amount of n-butyl lithium used) were added and reacted for 30 minutes, and then 0.064 parts of methanol was added as a polymerization terminator to give a conjugated diene series. A solution containing the polymer was obtained. Then, 100 parts of the obtained polymer component was treated with 2,4-bis [(octylthio) methyl] -o-cresol (trade name “Irganox 1520” manufactured by Ciba Specialty Chemicals) as an anti-aging agent.
  • 2,4-bis [(octylthio) methyl] -o-cresol trade name “Irganox 1520” manufactured by Ciba Specialty Chemicals
  • the resulting modified conjugated diene rubber 1 had a weight average molecular weight (Mw) of 478,000, and a coupling ratio of two or more branches was 38.3% by weight.
  • the temperature of the kneaded product at the end of kneading was 150 ° C. And after cooling the obtained kneaded material to room temperature, it knead
  • the obtained kneaded product was mixed with 1.40 parts of sulfur, a crosslinking accelerator: N-tert-butyl-2-benzothiazolylsulfenamide (trade name “Noxeller NS-P”, After adding 1.2 parts of Ouchi Shinsei Chemical Co., Ltd.) and 1.2 parts of diphenylguanidine (trade name “Noxeller D”, Ouchi Shinsei Chemical Co., Ltd.) and kneading them, a sheet-like rubber composition The thing was taken out. Next, the obtained rubber composition was press-crosslinked at 160 ° C. for 20 minutes to produce a rubber cross-linked test piece. The test piece was evaluated for low heat build-up and wet grip. The results are shown in Table 1.
  • Example 2 [Production of denaturant 2] Instead of 1-allyl-2,2 ′, 5,5′-tetramethyl- (1-aza-2,5-disilacyclopentane), N-allyl-N, N-bis (trimethylsilyl) amine 53. Except having used 3g, it carried out similarly to Example 1, and obtained the modifier 2 represented by following formula (9). The structure represented by the following formula (9) was also confirmed by 1 H-NMR. The viscosity of the obtained modifier 2 was measured at 25 ° C. according to JIS-Z-8803 using an Ubbelohde viscometer, and found to be 300 mm 2 / s.
  • the modified conjugated diene rubber when synthesizing the modified conjugated diene rubber, when the compound represented by the general formula (1) is used as a modifier, the modified conjugated diene rubber is obtained.
  • the rubber cross-linked products were all excellent in wet grip properties and low heat build-up (Examples 1 and 2).
  • a modified conjugated diene rubber is synthesized, even when a compound having a cyclic main chain structure composed of a repeating unit represented by —Si—O— is used as a modifier, a protected amino group-containing organic group In the case of using a material that does not have, the resulting rubber cross-linked product was inferior in wet grip and low heat build-up (Comparative Example 1).

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Abstract

L'invention concerne un procédé de production d'un caoutchouc diène conjugué modifié, le procédé comprenant une première étape de polymérisation, dans un solvant inerte, d'un monomère contenant au moins un composé diène conjugué par utilisation d'un composé organométallique actif en tant qu'amorceur de polymérisation, pour obtenir un polymère diène conjugué comportant une extrémité active, et une seconde étape de réaction d'un composé représenté par la formule générale (1) avec l'extrémité active dudit polymère diène conjugué comportant l'extrémité active. (Dans la formule générale (1), R1 et R3 représentent chacun d'une manière indépendante un groupe hydrocarboné monovalent, un atome d'hydrogène ou un groupe hydroxy, R2 représente un groupe organique défini arbitraire, un atome d'hydrogène ou un groupe hydroxy, X1 représente un groupe organique contenant un groupe amino protégé, contenant un groupe amino primaire protégé par un groupe protecteur, m représente un entier de 1 à 30, n représente un entier de 0 à 29, et m+n vaut 3 à 30.)
PCT/JP2017/040454 2016-11-14 2017-11-09 Procédé de production d'un caoutchouc diène conjugué modifié WO2018088483A1 (fr)

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Citations (5)

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JP2004231905A (ja) * 2003-01-31 2004-08-19 Nippon Zeon Co Ltd 共役ジエン系ゴムの製造方法
JP2010275489A (ja) * 2009-05-29 2010-12-09 Bridgestone Corp 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、ゴム組成物、空気入りタイヤ
JP2014501325A (ja) * 2010-12-31 2014-01-20 株式会社ブリヂストン カップリングされたポリマーおよびそれを製造する方法
JP2015521221A (ja) * 2012-05-09 2015-07-27 ランクセス・ドイチュランド・ゲーエムベーハー アミン含有カルビノール末端ポリマー
WO2016001372A1 (fr) * 2014-07-03 2016-01-07 Compagnie Generale Des Etablissements Michelin Elastomère diénique à ip réduit possédant une fonction silanol en extrémité de chaîne et composition le contenant

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US8030423B2 (en) 2008-01-25 2011-10-04 Salamone Joseph C Multi-armed macromonomers
JP7208795B2 (ja) 2016-11-14 2023-01-19 ダウ・東レ株式会社 共変性シリコーン

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004231905A (ja) * 2003-01-31 2004-08-19 Nippon Zeon Co Ltd 共役ジエン系ゴムの製造方法
JP2010275489A (ja) * 2009-05-29 2010-12-09 Bridgestone Corp 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、ゴム組成物、空気入りタイヤ
JP2014501325A (ja) * 2010-12-31 2014-01-20 株式会社ブリヂストン カップリングされたポリマーおよびそれを製造する方法
JP2015521221A (ja) * 2012-05-09 2015-07-27 ランクセス・ドイチュランド・ゲーエムベーハー アミン含有カルビノール末端ポリマー
WO2016001372A1 (fr) * 2014-07-03 2016-01-07 Compagnie Generale Des Etablissements Michelin Elastomère diénique à ip réduit possédant une fonction silanol en extrémité de chaîne et composition le contenant

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