WO2018181161A1 - Procédé de production d'un caoutchouc à base de diène conjugué modifié - Google Patents

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

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Publication number
WO2018181161A1
WO2018181161A1 PCT/JP2018/012105 JP2018012105W WO2018181161A1 WO 2018181161 A1 WO2018181161 A1 WO 2018181161A1 JP 2018012105 W JP2018012105 W JP 2018012105W WO 2018181161 A1 WO2018181161 A1 WO 2018181161A1
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conjugated diene
rubber
carbon atoms
group
compound
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PCT/JP2018/012105
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English (en)
Japanese (ja)
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岳史 杉村
山岸　英哲
辰夫 笹島
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日本ゼオン株式会社
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Priority to JP2019509789A priority Critical patent/JP7010285B2/ja
Publication of WO2018181161A1 publication Critical patent/WO2018181161A1/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
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F36/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F36/02—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F36/04—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
    • 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
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08L9/06—Copolymers with styrene

Definitions

  • the present invention relates to a modified conjugated diene rubber and a method for producing the same, and more particularly, to a modified conjugated diene rubber capable of providing a crosslinked rubber having excellent low heat buildup and high tensile strength, and a method for producing the same.
  • the present invention also relates to a rubber composition containing the modified conjugated diene rubber and a rubber cross-linked product thereof.
  • a tire obtained from a rubber composition blended with silica is superior in low heat build-up compared to a tire obtained from a rubber composition blended with commonly used carbon black. can do.
  • a rubber that is usually used is blended with silica, it is easy to separate because of its poor affinity with silica, and as a result, the fuel efficiency may be inferior.
  • Patent Document 1 a polyfunctional anionic polymerization initiator prepared by reacting a polyvinyl aromatic compound and an organolithium compound as a polymerization initiator, a conjugated diene compound and an aromatic vinyl compound are used. Modification reaction using a compound having a silyl group substituted with two or more alkoxy groups and one or more nitrogen atoms as a modifier at the terminal portion of the conjugated diene copolymer obtained by copolymerization There is disclosed a modified conjugated diene-based copolymer obtained by the above-mentioned process. In the technique of Patent Document 1, a polyfunctional anionic polymerization initiator is used as a polymerization initiator.
  • the polyfunctional anionic polymerization initiator is prepared by reacting a polyvinyl aromatic compound and an organolithium compound. Therefore, in addition to the lithiation reaction of vinyl groups, reactions between vinyl groups also occur, resulting in a three-dimensional structure. Therefore, the modified conjugated diene copolymer obtained using such a polyfunctional anionic polymerization initiator is also three-dimensionally cross-linked and thereby gelled. And the rubber cross-linked product obtained by using such a modified conjugated diene copolymer has a sufficient effect of improving low heat build-up by introducing a functional group having high affinity for silica due to the effect of gelation. It cannot be obtained, and furthermore, the tensile strength is inferior.
  • 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 provide a crosslinked rubber having excellent low heat buildup and high tensile strength. For the purpose.
  • an alkali metalated aromatic having two carbon atoms directly bonded to an alkali metal atom and an aromatic ring as a polymerization initiator.
  • a monomer comprising at least a conjugated diene compound is polymerized.
  • a conjugated diene rubber obtained by polymerization is subjected to a coupling reaction using a bifunctional coupling agent, and then coupled.
  • a modification conjugated diene rubber that can give a rubber cross-linked product having strength can be obtained, and has completed the present invention.
  • At least a conjugated diene compound is used as a polymerization initiator by using an alkali metalated aromatic compound having two carbon atoms directly bonded to an alkali metal atom and an aromatic ring in one molecule.
  • the modified conjugated diene rubber is reacted with a modifying agent having one atom or reactive group in one molecule capable of reacting with the active terminal at the active terminal of the conjugated diene rubber subjected to the coupling reaction.
  • a third step of obtaining a modified conjugated diene rubber is obtained by using an alkali metalated aromatic compound having two carbon atoms directly bonded to an alkali metal atom and an aromatic ring in one molecule.
  • the alkali metalated aromatic compound is obtained by reacting an organic alkali metal compound with an aromatic compound having two carbon atoms directly bonded to an aromatic ring in one molecule.
  • the aromatic compound having two carbon atoms directly bonded to the aromatic ring in one molecule is an aromatic compound represented by the following general formula (1) or the following general formula (2). Preferably there is.
  • n is an integer of 1 to 5
  • R 9 to R 18 each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R 9 to R 18 (When n is 2 or more, only two of R 9 , R 14 to R 18
  • the present invention also provides a modified conjugated diene rubber obtained by any one of the above production methods.
  • a modified conjugated diene rubber containing a modified conjugated diene polymer chain represented by the following general formula (3) is provided.
  • R 19 to R 24 are each independently an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, A hydroxyl group, a group represented by —NR 27 R 28 , or a group represented by —R 29 —NR 30 R 31 (R 27 , R 28 , R 30 , R 31 each independently represents 1 to 10 represents an alkyl group having 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, R 29 represents an alkylene group having 1 to 10 carbon atoms, Pol represents a polymer chain containing a conjugated diene monomer unit, and Arm represents Each independently represents a group represented by the following general formula (4) or (5), A 2 represents a silicon atom or a tin atom, and R 25 and R 26 each independently represents 1 carbon atom.
  • R 32 and R 33 each independently represents a hydrogen atom or an alkyl group having 1 to 9 carbon atoms
  • R 34 to R 39 are Each independently represents a hydrogen atom or an aryl group having 6 to 12 carbon atoms bonded directly or via an arbitrary linking group to the aromatic ring, wherein r is 1 to 5 in the general formula (5);
  • Integers R 40 and R 41 each independently represent a hydrogen atom or an alkyl group having 1 to 9 carbon atoms, and A 3 represents a chemical single bond or an arbitrary bond group.
  • 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 crosslinked rubber obtained by crosslinking the rubber composition, and a tire comprising the crosslinked rubber.
  • a modified conjugated diene rubber that can provide a crosslinked rubber having excellent low heat buildup and high tensile strength, a rubber composition containing the modified conjugated diene rubber, and the rubber composition It is possible to provide a rubber cross-linked product obtained by using a product, having excellent low exothermic property and high tensile strength.
  • the method for producing a modified conjugated diene rubber of the present invention uses, as a polymerization initiator, an alkali metalated aromatic compound having two carbon atoms directly bonded to an alkali metal atom and an aromatic ring in one molecule, A first step of polymerizing a monomer comprising at least a conjugated diene compound to obtain a conjugated diene rubber having an active end; A second step of performing a coupling reaction of the conjugated diene rubber having an active end using a bifunctional coupling agent; The modified conjugated diene rubber is reacted with a modifying agent having one atom or reactive group in one molecule capable of reacting with the active terminal at the active terminal of the conjugated diene rubber subjected to the coupling reaction. And obtaining a third step.
  • the first step in the production method of the present invention is at least conjugated using an alkali metalated aromatic compound having two carbon atoms in one molecule directly bonded to an alkali metal atom and an aromatic ring as a polymerization initiator.
  • a monomer comprising a diene compound is polymerized to obtain a conjugated diene rubber having an active end.
  • the polymerization initiator used in the first step of the production method of the present invention is an alkali metalated aromatic compound having two carbon atoms directly bonded to each of an alkali metal atom and an aromatic ring in one molecule.
  • the alkali metal atom of the alkali metalated aromatic compound used as a polymerization initiator in the present invention is not particularly limited, but is preferably lithium, sodium, or potassium, and among these, lithium is Particularly preferred.
  • the aromatic ring of the alkali metalated aromatic compound is not particularly limited as long as it is a conjugated ring having aromaticity, and specific examples include electrically neutral such as a benzene ring, a naphthalene ring, and an anthracene ring.
  • An aromatic hydrocarbon ring an aromatic hydrocarbon ring having a negative charge such as a cyclopentadienyl anion ring, an indenyl anion ring or a fluorenyl anion ring; an aromatic ring containing a heteroatom such as a furan ring or a thiophene ring; And so on.
  • an electrically neutral aromatic hydrocarbon ring is preferable, and a benzene ring is particularly preferable.
  • An alkali metalated aromatic compound having an electrically neutral aromatic hydrocarbon ring is preferably used from the viewpoint of its stability and polymerization activity.
  • the alkali metal atom is usually present in a cation state in the alkali metalated aromatic compound, and the alkali metal atom and the aromatic ring
  • the carbon atom directly bonded to each of the carbon atoms is usually present in an anionic state in order to bind to the alkali metal atom in such a cation state.
  • the alkali metal atom thus present in the cation state and the carbon atom present in the anion state form an ionic bond, thereby directly connecting each other. It is in a combined state.
  • an alkali metalated aromatic compound having two carbon atoms in one molecule directly bonded to each of an alkali metal atom and an aromatic ring is used as a polymerization initiator. Since the conjugated diene polymer chain grows with living polymerizability, starting from each of the carbon atoms directly bonded to the two alkali metal atoms contained in the compound, the resulting conjugated diene rubber Can have a linear structure starting from an alkali metalated aromatic compound.
  • the alkali metalated aromatic compound used as a polymerization initiator in the present invention has two carbon atoms directly bonded to each of an alkali metal atom and an aromatic ring in its molecule, its structure is There is no particular limitation. For example, even if two carbon atoms directly bonded to an alkali metal atom are directly bonded to one aromatic ring, one carbon atom directly bonded to the alkali metal atom is directly bonded.
  • the two aromatic rings may be provided, and such aromatic rings may be bonded via a chemical single bond or a bonding group.
  • a compound represented by the following general formula (6) is preferably used as an alkali metalated aromatic compound in which two carbon atoms directly bonded to an alkali metal atom are directly bonded to one aromatic ring.
  • s is an integer of 0 to 5
  • R 42 to R 49 are each independently an alkali metal having 1 to 10 carbon atoms in which a hydrogen atom and an alkali metal atom are bonded to the ⁇ -position.
  • a 4 is preferably a chemical single bond or an alkylene group having 1 to 5 carbon atoms, and more preferably a chemical single bond or a methylene group.
  • t is preferably an integer of 1 to 2, and more preferably 1.
  • Examples of the aromatic compound having two carbon atoms directly bonded to the aromatic ring in one molecule that can be used in the synthesis of the alkali metalated aromatic compound include the alkali metalated aromatic compound represented by the general formula (6).
  • An aromatic compound represented by the following general formula (2) can be exemplified.
  • the alkyl group having 1 to 10 carbon atoms is more preferably an alkyl group having 1 to 5 carbon atoms, and further preferably a methyl group.
  • the aryl group having 6 to 12 carbon atoms bonded to the aromatic ring directly or via any bonding group includes a phenyl group bonded directly to the aromatic ring or via an alkylene group having 1 to 6 carbon atoms. A phenyl group bonded to an aromatic ring directly or via a methylene group is more preferable.
  • groups other than alkyl groups having 1 to 10 carbon atoms include hydrogen atoms or 6 to 12 carbon atoms bonded to an aromatic ring directly or via any bonding group. Any of aryl groups may be used, but a hydrogen atom is preferable.
  • m is preferably an integer of 0 to 2, and more preferably 0.
  • the method of reacting the organic alkali metal compound with the aromatic compound having two carbon atoms directly bonded to the aromatic ring in the molecule is not particularly limited, but the reaction is performed in an inert solvent under an inert atmosphere. Is preferably used.
  • the inert solvent used is not particularly limited as long as it can dissolve the compound to be reacted, but a hydrocarbon solvent is preferably used. Specific examples include aliphatic hydrocarbons such as n-hexane, n-heptane, and n-octane; alicyclic hydrocarbons such as cyclohexane, cyclopentane, and methylcyclohexane.
  • these solvents may be used individually by 1 type, and 2 or more types may be mixed and used for them.
  • the amount of the organic alkali metal compound used for the aromatic compound having two carbon atoms directly bonded to the aromatic ring in the molecule is not particularly limited, but it is directly bonded to the aromatic ring in the aromatic compound.
  • the amount is usually 0.1 to 100 mol, preferably 0.2 to 50 mol, more preferably 0.3 to 10 mol, particularly preferably 0.3 to 1.5 mol, per 1 mol of carbon atoms.
  • the reaction time and reaction temperature of this reaction are not particularly limited, but the reaction time is usually in the range of 1 minute to 10 days, preferably 1 minute to 5 days, and the reaction temperature is usually in the range of ⁇ 50 ° C. to 100 ° C. It is.
  • the amount of the compound having the coordination ability to the alkali metal atom is not particularly limited, and may be determined according to the strength of the coordination ability.
  • a compound having a coordination ability to an alkali metal atom a chain ether compound that is a relatively weak coordination ability or a tertiary amine compound having one nitrogen atom in the molecule is used.
  • the amount used is usually in the range of 1 to 100 mol, preferably 5 to 50 mol, more preferably 10 to 25 mol, per mol of the alkali metal atom in the organic alkali metal compound to be reacted with the aromatic compound. .
  • a cyclic ether compound or nitrogen-containing heterocyclic compound having one oxygen atom in the molecule as a compound having a coordination ability to an alkali metal atom
  • the amount used is usually in the range of 1 to 100 moles, preferably 1 to 20 moles, more preferably 2 to 10 moles per mole of alkali metal atoms in the organic alkali metal compound to be reacted with the aromatic compound.
  • the reaction may not proceed.
  • the compound which has the coordination ability to these alkali metal atoms may be used individually by 1 type, and may be used in combination of 2 or more type.
  • the production efficiency of the alkali metalated aromatic compound having two carbon atoms directly bonded to the alkali metal atom and the aromatic ring in one molecule is particularly good, and the linear chain in the conjugated diene rubber obtained by polymerization is used.
  • a compound having the ability to coordinate to an alkali metal atom a cyclic ether compound having two or more oxygen atoms in the molecule, a tertiary having two or more nitrogen atoms in the molecule
  • a range of 0.02 to 3 moles per 1 mole of atoms is particularly preferred.
  • the order of addition is not particularly limited.
  • an aromatic compound and an organic alkali metal compound are allowed to coexist, and then a compound capable of coordinating to an alkali metal atom is added to the system.
  • the order in which the organic alkali metal compound is added to the system after the coexistence of the aromatic compound and the compound having the ability to coordinate to the alkali metal atom is preferred. By adding in this order, insolubilization due to complex formation between the organic alkali metal compound and the compound capable of coordinating to the alkali metal atom is prevented, and the production efficiency of the alkali metalated aromatic compound is particularly good. Become.
  • the alkali metalated aromatic compound having two carbon atoms directly bonded to an alkali metal atom and an aromatic ring, obtained as described above, in one molecule Is used as a polymerization initiator to polymerize a monomer comprising at least a conjugated diene compound, thereby obtaining a conjugated diene rubber having an active terminal.
  • the polymerization initiators described above may be used alone or in combination of two or more.
  • the conjugated diene compound is not particularly limited.
  • 1,3-butadiene, isoprene or 1,3-pentadiene is preferable, and 1,3-butadiene and isoprene are particularly preferable.
  • 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 rubber having an active end is preferably obtained by copolymerizing a monomer containing 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, and the like.
  • the conjugated diene rubber having an active terminal used in the present invention preferably contains 50 to 100% by weight of a conjugated diene monomer unit, particularly preferably contains 55 to 95% by weight, and an aromatic vinyl monomer. Those containing 50 to 0% by weight of monomer units are preferred, and those containing 45 to 5% by weight are particularly preferred.
  • the conjugated diene rubber having an active end may contain other monomers as desired in addition to the conjugated diene compound and the aromatic vinyl compound as long as the object of the present invention is not impaired. May be obtained by copolymerization.
  • 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 other monomers are preferably 10% by weight or less, more preferably 5% by weight or less as monomer units in the conjugated diene rubber having an active end.
  • the mode of copolymerization is not particularly limited, and any of random, block, and tapered shapes may be used. Although it is good, a random binding mode is preferable. By making it random, the resulting rubber cross-linked product becomes superior due to its low heat build-up.
  • the use ratio of the alkali metalated aromatic compound and the monomer used as the polymerization initiator to the molecular weight of the target polymer since the polymerization reaction usually proceeds with living properties, the use ratio of the alkali metalated aromatic compound and the monomer used as the polymerization initiator to the molecular weight of the target polymer.
  • the amount of alkali metal in the alkali metalated aromatic compound relative to 1 mol of the monomer is usually 0.000001 to 0.1 mol, preferably 0.00001 to 0.05 mol, Particularly preferably, it is selected in the range of 0.0001 to 0.01 mol. If the amount of the alkali metalated aromatic compound used is too small, the molecular weight of the resulting conjugated diene rubber will be too high, making it difficult to handle, and the polymerization reaction may not proceed sufficiently. On the other hand, if the amount of the alkali metalated aromatic compound used is too large, the molecular weight of the resulting conjugated diene rubber will be too low, and the rubber material
  • a compound having the ability to coordinate to the alkali metal atom as described above is added to the polymerization reaction system for the purpose of controlling the polymerization rate and the microstructure of the resulting conjugated diene rubber. May be.
  • the amount of the compound having a coordination ability to the alkali metal atom is usually 5 mol or less, preferably 4 mol, per 1 mol of the alkali metal atom in the alkali metalated aromatic compound used as the polymerization initiator. Hereinafter, it is particularly preferably 2 mol or less. If the amount of the compound having coordination ability to these alkali metal atoms is too large, the polymerization reaction may be inhibited.
  • the solution containing the compound when preparing the alkali metalated aromatic compound used as a polymerization initiator, when using the compound which has the coordination ability to an alkali metal atom, the solution containing the compound can also be used as it is.
  • the resulting rubber cross-linked product can be made more excellent in low heat build-up, a cyclic ether compound having two or more oxygen atoms in the molecule, and a tertiary class having two or more nitrogen atoms in the molecule.
  • an alkali metal compound using at least one compound selected from an amine compound and a tertiary amide compound having a nitrogen-heteroatom bond in the molecule as a polymerization initiator (the alkali metal compound here is an alkali metalation compound) Not limited to aromatic compounds, present in the reaction system and includes all alkali metal compounds that act as polymerization initiators)) in the range of 0.02 to 3.0 moles per mole of alkali metal atoms It is preferable to make it. By doing in this way, the conjugated diene rubber
  • a solution polymerization method is preferably used as the polymerization mode of the monomer containing the conjugated diene compound.
  • the solvent used in the solution polymerization method is not particularly limited as long as it is inactive in the polymerization reaction and can dissolve the monomer and the polymerization catalyst.
  • Specific examples of the solvent that can be used include aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene; aliphatic hydrocarbons such as n-hexane, n-heptane, and n-octane; cyclohexane, cyclopentane, and methylcyclohexane.
  • ethers such as tetrahydrofuran, diethyl ether and cyclopentyl methyl ether;
  • an aliphatic hydrocarbon or alicyclic hydrocarbon as a solvent because the polymerization activity becomes high.
  • these solvents may be used individually by 1 type, and 2 or more types may be mixed and used for them.
  • the concentration of the monomer in the polymerization solution in the solution polymerization method is not particularly limited, but is usually selected in the range of 1 to 50% by weight, preferably 2 to 45% by weight, more preferably 5 to 40% by weight. If the concentration of the monomer in the solution is too low, the productivity of the conjugated diene rubber may be deteriorated. If the concentration is too high, the viscosity of the solution may become too high and handling thereof may be difficult. is there.
  • the polymerization temperature is not particularly limited, but is usually in the range of ⁇ 30 ° C. to + 200 ° C., preferably 0 ° C. to + 180 ° C.
  • the polymerization time is not particularly limited, and is usually in the range of 1 minute to 100 hours.
  • any of batch mode and continuous mode can be adopted.
  • a conjugated diene monomer unit and an aromatic vinyl monomer unit are used.
  • the batch method is preferable in that the randomness of the bond can be easily controlled.
  • a conjugated diene rubber can be obtained by polymerizing a monomer containing a conjugated diene compound.
  • the polymerization reaction usually proceeds with a living property, so that a polymer having an active end exists in the polymerization reaction system. Therefore, in the first step, the conjugated diene rubber obtained by the polymerization reaction has an active end.
  • an alkali metalated aromatic compound having two carbon atoms directly bonded to each of an alkali metal atom and an aromatic ring is used as a polymerization initiator.
  • the conjugated diene rubber having an active end obtained in the step has a linear structure starting from an alkali metalated aromatic compound.
  • the second step in the production method of the present invention is a step of performing a coupling reaction of the conjugated diene rubber having an active end obtained in the first step using a bifunctional coupling agent.
  • the conjugated diene rubber having an active end obtained in the first step has a linear structure as described above. Therefore, according to the second step of the production method of the present invention, a coupling reaction is performed on such a linear conjugated diene rubber having an active end using a bifunctional coupling agent. Thus, it becomes possible to increase the molecular weight by a coupling reaction while maintaining the linear structure. Further, according to the second step of the production method of the present invention, it is possible to increase the molecular weight while maintaining the linear structure, thereby effectively suppressing gelation due to three-dimensionalization, The molecular weight can be realized.
  • the bifunctional coupling agent is not particularly limited as long as it is a compound having two functional groups capable of reacting with the active end of a conjugated diene rubber having an active end in one molecule.
  • Such bifunctional coupling agents include dihalosilane compounds such as dimethyldichlorosilane, diethyldichlorosilane, dipropyldichlorosilane, dibutyldichlorosilane, diphenyldichlorosilane; dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, Dialkoxysilane compounds such as diethyldiethoxysilane, dipropyldimethoxysilane, dipropyldiethoxysilane, dibutyldimethoxysilane, dibutyldiethoxysilane, methylethyldimethoxysilane, methylethyldiethoxysilane, diphenyldime
  • these bifunctional coupling agents may be used individually by 1 type, and may be used in combination of 2 or more type.
  • dihalosilane compounds and dialkoxysilane compounds are preferable from the viewpoint of reactivity, and dichlorosilane compounds and dialkoxysilane compounds are more preferable.
  • dihalosilane compound and the dihalotin compound two halogen atoms correspond to the functional group capable of reacting with the active end of the conjugated diene rubber having the active end.
  • dialkoxysilane compound and the dialkoxytin compound Corresponds to a functional group in which two alkoxyl groups can react with the active end of a conjugated diene rubber having an active end.
  • the amount of the bifunctional coupling agent used is not particularly limited, but is 0 with respect to 1 mol of the alkali metal atom in the alkali metalated aromatic compound used as the polymerization initiator.
  • the amount is preferably in the range of 0.001 to 1.0 mol, more preferably 0.01 to 0.5 mol, and more preferably 0.05 to 0.3 mol. Is particularly preferred.
  • a method in which a conjugated diene rubber having an active end obtained in the first step described above is reacted with a bifunctional coupling agent, thereby causing a coupling reaction is not particularly limited, there is a method of mixing the conjugated diene rubber having an active end obtained in the first step described above and a bifunctional coupling agent in a solvent capable of dissolving them. Can be mentioned.
  • the solvent used in this case those exemplified as the solvent used for the polymerization of the conjugated diene rubber described above can be used.
  • the conjugated diene rubber having an active end obtained in the first step is kept in the state of the polymerization solution used for the polymerization, and a bifunctional coupling agent is added thereto.
  • the method is simple and preferable.
  • the reaction temperature in the second step is not particularly limited, but is usually 0 to 120 ° C., and the reaction time is not particularly limited, but is usually 1 minute to 1 hour.
  • the time when the bifunctional coupling agent is added to the solution containing the conjugated diene rubber having an active end is not particularly limited, but the polymerization reaction is not completed, and the conjugated diene rubber having an active end is added.
  • a state in which the solution containing the monomer also contains a monomer, more specifically, a solution containing a conjugated diene rubber having an active end is 100 ppm or more, more preferably 300 to 50,000 ppm. It is desirable to add a bifunctional coupling agent to this solution in the state of containing the. By adding the bifunctional coupling agent in this way, side reactions between the conjugated diene rubber having an active terminal and impurities contained in the polymerization system can be suppressed, and the reaction can be controlled well. It becomes possible.
  • the active end reacted with the bifunctional coupling agent reacts with the bifunctional coupling agent, Forms a chemical bond with the bifunctional coupling agent, thereby deactivating.
  • the active terminal that has not reacted with the bifunctional coupling agent remains while maintaining its reaction activity.
  • one atom or reactive group capable of reacting with such an active end is present per active molecule of the conjugated diene rubber subjected to the coupling reaction in the second step. It is possible to modify the conjugated diene rubber by reacting it with a modifying agent (hereinafter referred to as “monofunctional modifying agent” as appropriate), thereby improving the affinity for fillers such as silica.
  • a modifying agent hereinafter referred to as “monofunctional modifying agent” as appropriate
  • the rubber cross-linked product obtained by blending with a crosslinking agent or the like can be excellent in low exothermic property and have high tensile strength.
  • the conjugated diene rubber having a high molecular weight linear active terminal is used.
  • the polymer chain ends can be modified while maintaining the straight chain structure, which effectively reduces the gelation due to the three-dimensionalization, while maintaining the straight chain structure.
  • a modifying group can be appropriately introduced into the terminal of the chain conjugated diene rubber. And, by introducing such a modifying group, it is possible to dramatically improve the affinity with a filler and the like, and thereby, low heat generation when a filler such as silica is blended into a rubber cross-linked product.
  • the rubber cross-linked product can have a high tensile strength due to the effect of increasing the molecular weight.
  • the monofunctional modifier used in the third step is not particularly limited, but a silane compound having one atom or reactive group capable of reacting with the active terminal in one molecule is preferable.
  • the atom or reactive group capable of reacting with the active terminal of the conjugated diene rubber is not particularly limited as long as it can react with the active terminal, but from the viewpoint of reactivity with the active terminal, a halogen atom , A vinyl group, an alkoxyl group, a carbonyl group or an epoxy group are preferred, an epoxy group, an alkoxy group or a halogen atom is more preferred, a halogen atom is further preferred, and a chlorine atom is particularly preferred.
  • silane compound it is preferable that a silicon atom contained in the molecule is bonded to one or more hydroxyl-protecting groups, thereby more appropriately increasing the affinity for a filler such as silica. As a result, the low exothermic property and tensile strength of the resulting rubber cross-linked product can be further improved.
  • a hydroxyl-protecting group is a group capable of giving a hydroxyl group by hydrolysis. Therefore, hydrolysis of such a hydroxyl-protecting group includes a hydroxyl group at the terminal of the conjugated diene rubber.
  • a modifying group can be introduced.
  • the hydroxyl-protecting group is preferably one that acts as a hydroxyl-protecting group and does not exhibit reactivity (or very low reactivity) with respect to the active terminal of the conjugated diene rubber.
  • R a and R b are each independently an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, preferably An alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms, and particularly preferably a methyl group or an ethyl group.
  • a silane compound represented by the following general formula (8) is preferably used as the monofunctional modifier.
  • X reacts with an atom or a reactive group capable of reacting with an active end of a conjugated diene rubber having an active end, or with an active end of a conjugated diene rubber having an active end.
  • R 60 , R 61 , R 62 , R 64 , R 65 are each independently an alkyl group having 1 to 10 carbon atoms or a carbon number An aryl group having 6 to 12 carbon atoms, and R 63 represents an alkylene group having 1 to 10 carbon atoms.
  • a is an integer of 0 to 3
  • b is an integer of 0 to 3
  • c is an integer of 0 to 3
  • a + b + c 3.
  • the atom or reactive group capable of reacting with the active terminal of the conjugated diene rubber is, from the viewpoint of reactivity with respect to the active terminal, a halogen atom, vinyl group, alkoxyl group, amino group or epoxy. Group is preferred, an epoxy group or a halogen atom is more preferred, a halogen atom is further preferred, and a chlorine atom is particularly preferred.
  • the hydrocarbon group containing any one of an atom and a reactive group that can react with the active end of the conjugated diene rubber having an active end is not particularly limited. A hydrocarbon group having 1 to 10 carbon atoms containing any one of such atoms and reactive groups is preferred. This carbon number does not include the number of carbons constituting the reactive group.
  • R 60 , R 61 , R 62 , R 64 and R 65 are an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, preferably a carbon number
  • R 63 is an alkylene group having 1 to 10 carbon atoms, preferably an alkylene group having 1 to 5 carbon atoms.
  • a is an integer of 0 to 3
  • b is an integer of 0 to 3
  • c is an integer of 0 to 3
  • a + b + c 3.
  • the compound represented by the general formula (8) has at least a group represented by —NR 61 R 62 , thereby more appropriately increasing the affinity for a filler such as silica.
  • the group represented by —NR 61 R 62 acts as a hydroxyl-protecting group.
  • the usage-amount of a monofunctional modifier in a 3rd process is not specifically limited,
  • the amount of atoms or reactive groups that can be reacted is preferably in the range of 0.05 to 5 mol, more preferably 0.1 to 3 mol, more preferably 0.2 to It is particularly preferable that the amount be 1.5 mol.
  • a monofunctional modifier may be used individually by 1 type, and may be used in combination of 2 or more type.
  • the method of reacting the monofunctional modifier with the active end of the conjugated diene rubber that has undergone the coupling reaction in the second step is not particularly limited.
  • examples thereof include a method of mixing the conjugated diene rubber subjected to the coupling reaction in the second step and the monofunctional modifier in a solvent capable of dissolving them.
  • the solvent used in this case those exemplified as the solvent used in the polymerization and coupling reaction of the conjugated diene rubber described above can be used.
  • the method of adding the monofunctional modifier to the conjugated diene rubber that has undergone the coupling reaction in the second step as it is in the polymerization solution used for the polymerization is also simple. It is preferable.
  • the reaction temperature in the third step is not particularly limited, but is usually 0 to 120 ° C., and the reaction time is not particularly limited, but is usually 1 minute to 1 hour.
  • the time when the monofunctional modifier is added to the solution containing the conjugated diene rubber that has undergone the coupling reaction is not particularly limited, but the polymerization reaction has not been completed, and the conjugated diene system in which the coupling reaction has been performed.
  • the rubber-containing solution also contains a monomer, more specifically, the solution containing the conjugated diene rubber subjected to the coupling reaction is 100 ppm or more, more preferably 300 to 50,000 ppm. It is desirable to add a monofunctional modifier to this solution in the state of containing the monomer. By adding the monofunctional modifier in this way, side reactions between the conjugated diene rubber and impurities contained in the polymerization system can be suppressed, and the reaction can be controlled well.
  • 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 can be obtained by removing a rubber from a solution, such as reprecipitation, solvent removal under heating, solvent removal under reduced pressure, or solvent removal with steam (steam stripping). It can be separated and obtained from the reaction mixture by a normal operation during separation.
  • a silane compound having a hydroxyl-protecting group specifically, a silane compound represented by the above general formula (8), and —NR 61 R 62
  • a compound having a group represented when the solvent is removed by steam stripping, at least a part of these groups is hydrolyzed to form a hydroxyl group.
  • the modified conjugated diene rubber of the present invention thus obtained has a linear structure with a high molecular weight, and since it has a linear structure, it is gelled by three-dimensionalization. Is effectively suppressed, and the dispersibility of fillers such as silica can be enhanced by the effect of the linear structure, the effect of increasing the molecular weight, and the effect of introducing a terminal modifying group, Thereby, when a filler such as silica is blended to form a rubber cross-linked product, the low heat build-up property can be excellent, and the obtained rubber cross-linked product also has high tensile strength. It is something that can be done.
  • the modified conjugated diene rubber of the present invention contains a modified conjugated diene polymer chain represented by the following general formula (3).
  • the method for producing the modified conjugated diene rubber of the present invention is not particularly limited, but it is preferable to follow the production method of the present invention (through the first to third steps) as described above.
  • R 19 to R 24 are each independently an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, a hydroxyl group , —NR 27 R 28 , or —R 29 —NR 30 R 31 (R 27 , R 28 , R 30 , R 31 are each independently a group having 1 to 10 carbon atoms, Or an aryl group having 6 to 12 carbon atoms, R 29 is an alkylene group having 1 to 10 carbon atoms, and at least one of R 19 to R 21 is a hydroxyl group or —NR 27 R 28 .
  • R 22 to R 24 is a hydroxyl group or a group represented by —NR 27 R 28 .
  • Pol represents a polymer chain containing a conjugated diene monomer unit
  • Arm represents each independently a group represented by the following general formula (4) or (5)
  • a 2 represents silicon.
  • R 25 and R 26 each independently represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms.
  • q is an integer of 0 to 5, preferably an integer of 0 to 2, and more preferably 0.
  • R 32 and R 33 each independently represents a hydrogen atom or an alkyl group having 1 to 9 carbon atoms, preferably a hydrogen atom.
  • R 34 to R 39 each independently represents a hydrogen atom or an aryl group having 6 to 12 carbon atoms bonded to the aromatic ring directly or via any bonding group, and preferably R 34 to R 39. Is a hydrogen atom.
  • the aryl group having 6 to 12 carbon atoms bonded directly or via an arbitrary linking group to the aromatic ring includes a phenyl group bonded directly to the aromatic ring or via an alkylene group having 1 to 6 carbon atoms.
  • a phenyl group bonded to an aromatic ring directly or via a methylene group is more preferable.
  • r is an integer of 1 to 5, preferably an integer of 0 to 2, and more preferably 1.
  • R 40 and R 41 each independently represents a hydrogen atom or an alkyl group having 1 to 9 carbon atoms, preferably a hydrogen atom.
  • a 3 represents any bonding group, preferably a chemical single bond or an alkylene group having 1 to 5 carbon atoms, and more preferably a chemical single bond or a methylene group.
  • a silane compound having a hydroxyl protecting group Specifically, a silane compound represented by the above general formula (8) and having a group represented by —NR 61 R 62 is used, and at least a part of these groups is hydrolyzed.
  • a hydroxyl group may be obtained by decomposing.
  • a method of hydrolysis when the modified conjugated diene rubber after the modification reaction is separated from the solution, the solvent is removed by steam stripping, so that the modified conjugated diene rubber after the modification reaction is removed. Along with separation from the solution, a hydroxyl group can be introduced by hydrolyzing at least a part of these groups.
  • the weight average molecular weight of the modified conjugated diene rubber of the present invention is not particularly limited, but is usually 500,000 to 3,000,000, preferably 750,000 as a value measured by gel permeation chromatography in terms of polystyrene. Those having a high molecular weight in the range of ⁇ 2,750,000, more preferably in the range of 1,000,000 to 2,500,000.
  • By setting the weight average molecular weight of the modified conjugated diene rubber to the above range low heat build-up and tensile strength can be further improved.
  • the molecular weight distribution represented by the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the modified conjugated diene rubber of the present invention is not particularly limited, but preferably 1.1 to 5.0, particularly preferably 1.2 to 3.0.
  • the Mooney viscosity (ML1 + 4 , 100 ° C.) of the modified conjugated diene rubber of the present invention is not particularly limited, but is usually in the range of 20 to 250, preferably 30 to 200. 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 vinyl bond content in the conjugated diene unit portion of the modified conjugated diene rubber of the present invention is usually 1 to 80 mol%, preferably 5 to 75 mol%.
  • 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 the rubber component containing the above-described modified conjugated diene rubber of the present invention.
  • 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) propyl) tetrasulfide, ⁇ -trimethoxysilylpropyldimethylthiocarbamyl tetrasulfide, and ⁇ -Trimethoxysilylpropylbenzothiazyl tetrasulfide and the like.
  • These silane coupling agents can be used alone
  • 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 contain other rubbers other than the above-described modified conjugated diene rubber of the present invention.
  • other rubbers include natural rubber, polyisoprene rubber, emulsion-polymerized styrene-butadiene copolymer rubber, solution-polymerized styrene-butadiene copolymer rubber, polybutadiene rubber (polybutadiene containing crystal fibers made of 1,2-polybutadiene polymer).
  • Styrene-isoprene copolymer rubber butadiene-isoprene copolymer rubber, styrene-isoprene-butadiene copolymer rubber, acrylonitrile-butadiene copolymer rubber, acrylonitrile-styrene-butadiene copolymer rubber, and the like.
  • 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 of the present invention preferably accounts for 10 to 100% by weight, particularly preferably 50 to 100% by weight, of the rubber component in the rubber composition.
  • the modified conjugated diene rubber of the present invention in the rubber component at such a ratio, it is possible to obtain a crosslinked rubber having excellent low heat buildup and high tensile strength.
  • 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 100 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 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 using the above-described modified conjugated diene rubber of the present invention, and therefore has excellent low heat buildup and high tensile strength.
  • the modified conjugated diene rubber of the present invention since the modified conjugated diene rubber of the present invention has a linear structure with a high molecular weight, gelation due to three-dimensionalization is effectively suppressed because it has a linear structure.
  • the dispersibility of fillers such as silica can be enhanced by the effect of the linear structure, the effect of increasing the molecular weight, and the effect of introducing a terminal modifying group.
  • the low heat build-up property can be excellent, and the resulting rubber cross-linked product can also have high tensile strength. is there.
  • 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 low heat build-up and has high tensile strength, so that it can be suitably used as a tire material, particularly a low fuel consumption tire material.
  • the yellow oily liquid was subjected to gas chromatograph mass spectrometry (GC-MS).
  • GC-MS gas chromatograph mass spectrometry
  • this yellow oily liquid was subjected to 1 H-NMR measurement.
  • the lithiation rate of the methyl group of m-xylene was 81%, and the average number of lithium atoms introduced into one molecule of m-xylene. was 1.63.
  • the yellow oily liquid was subjected to gas chromatograph mass spectrometry (GC-MS).
  • GC-MS gas chromatograph mass spectrometry
  • this yellow oily liquid was subjected to 1 H-NMR measurement.
  • the lithiation rate of the methyl group of p-xylene was 76%, and the average number of lithium atoms introduced into one molecule of p-xylene. was 1.51.
  • the yellow oily liquid was subjected to gas chromatograph mass spectrometry (GC-MS).
  • GC-MS gas chromatograph mass spectrometry
  • this yellow oily liquid was subjected to 1 H-NMR measurement.
  • the lithiation rate of methyl group of 4,4′-dimethylbiphenyl was 85%, and one molecule of 4,4′-dimethylbiphenyl.
  • the average number of lithium atoms introduced into was 1.70.
  • the yellow oily liquid was subjected to gas chromatograph mass spectrometry (GC-MS).
  • GC-MS gas chromatograph mass spectrometry
  • this yellow oily liquid was subjected to 1 H-NMR measurement.
  • the lithiation rate of the methyl group of di-p-tolylmethane was 81% and was introduced into one molecule of di-p-tolylmethane.
  • the average number of lithium atoms was 1.62.
  • the yellow oily liquid was subjected to gas chromatograph mass spectrometry (GC-MS).
  • GC-MS gas chromatograph mass spectrometry
  • Example 1 [Production of terminal-modified styrene-butadiene rubber 1] Under a nitrogen atmosphere, 800 parts of cyclohexane, 94.8 parts of 1,3-butadiene, 25.2 parts of styrene, and 0.207 parts of tetramethylethylenediamine were charged in an autoclave, and then the polymerization initiator obtained in Production Example 1 was obtained. 0.746 parts of a solution of 1 (amount of tetramethylethylenediamine present in the reaction system is 2.0 mol per mol of n-butyllithium used in the production of the polymerization initiator 1), 60 Polymerization was started at 0 ° C.
  • the polymerization reaction was continued for 60 minutes, and after confirming that the polymerization conversion was in the range of 95% to 100%, 0.011 part of dimethyldichlorosilane was added and allowed to react for 15 minutes. Furthermore, after adding 0.059 part of dimethyl (dimethylamino) chlorosilane and making it react for 30 minutes, the solution containing the modified styrene butadiene rubber 1 was obtained by adding 0.064 part of methanol as a polymerization terminator. .
  • the obtained modified styrene butadiene rubber 1 has a number average molecular weight (Mn) of 983,000, a weight average molecular weight (Mw) of 1,278,000, and a molecular weight distribution (Mw / Mn) of 1.30 in GPC measurement. It was a thing.
  • the modified styrene butadiene rubber 1 had a styrene unit content of 21.5 mol% and a vinyl bond content in the butadiene unit of 60.2 mol%. Further, when this modified styrene butadiene rubber 1 was subjected to 1 H-NMR measurement, it was confirmed that a dimethylsilanol group was introduced.
  • the temperature of the kneaded product at the end of kneading was 150 ° C. After the kneaded product was cooled to room temperature, it was kneaded again in a Brabender type mixer at 110 ° C. for 2 minutes, and then the kneaded product was discharged from the mixer.
  • Example 2 Instead of 0.011 part of dimethyldichlorosilane, 0.010 part of dimethyldimethoxysilane was used, and 0.084 part of tris (dimethylamino) chlorosilane was used instead of 0.059 part of dimethyl (dimethylamino) chlorosilane.
  • the modified styrene butadiene rubber 2 was produced in the same manner as in Example 1 except for the above.
  • the obtained modified styrene butadiene rubber 2 has a number average molecular weight (Mn) of 893,000, a weight average molecular weight (Mw) of 1,197,000, and a molecular weight distribution (Mw / Mn) of 1.34 in GPC measurement.
  • the modified styrene butadiene rubber 2 had a styrene unit content of 21.4 mol% and a vinyl bond content in the butadiene unit of 60.3 mol%. Furthermore, when this modified styrene butadiene rubber 2 was subjected to 1 H-NMR measurement, it was confirmed that a silanetriol group was introduced.
  • the modified styrene butadiene rubber 2 obtained above was used in the same manner as in Example 1 to prepare a rubber composition and prepare a test piece of a rubber cross-linked product. And evaluated in the same manner. The results are shown in Table 1.
  • Example 3 Modified styrene butadiene rubber 3 in the same manner as in Example 1 except that 0.746 part of the solution of polymerization initiator 2 obtained in Production Example 2 was used instead of 0.746 part of the solution of polymerization initiator 1.
  • the obtained modified styrene butadiene rubber 3 has a number average molecular weight (Mn) of 916,000, a weight average molecular weight (Mw) of 1,200,000, and a molecular weight distribution (Mw / Mn) of 1.31 in GPC measurement. It was a thing.
  • the modified styrene-butadiene rubber 3 had a styrene unit content of 20.9 mol% and a vinyl bond content in the butadiene unit of 59.3 mol%. Furthermore, when this modified styrene butadiene rubber 3 was subjected to 1 H-NMR measurement, it was confirmed that a dimethylsilanol group was introduced.
  • the modified styrene butadiene rubber 3 obtained above was used in the same manner as in Example 1 to prepare a rubber composition and prepare a test piece of a crosslinked rubber product. And evaluated in the same manner. The results are shown in Table 1.
  • Example 4 Modified styrene butadiene rubber 4 in the same manner as in Example 1 except that 0.762 part of the polymerization initiator 3 solution obtained in Production Example 3 was used instead of 0.746 part of the polymerization initiator 1 solution.
  • the obtained modified styrene butadiene rubber 4 has a number average molecular weight (Mn) of 1,018,000, a weight average molecular weight (Mw) of 1,313,000, and a molecular weight distribution (Mw / Mn) of 1 in GPC measurement. 29.
  • the modified styrene butadiene rubber 4 had a styrene unit content of 21.1 mol% and a vinyl bond content in the butadiene unit of 59.9 mol%. Furthermore, when this modified styrene butadiene rubber 4 was subjected to 1 H-NMR measurement, it was confirmed that a dimethylsilanol group was introduced.
  • the modified styrene butadiene rubber 4 obtained above was used in the same manner as in Example 1 to prepare a rubber composition and prepare a test piece of a crosslinked rubber product. And evaluated in the same manner. The results are shown in Table 1.
  • Example 5 Modified styrene butadiene rubber 5 in the same manner as in Example 1 except that 0.765 part of the solution of polymerization initiator 4 obtained in Production Example 4 was used instead of 0.746 part of the solution of polymerization initiator 1.
  • the obtained modified styrene butadiene rubber 5 has a number average molecular weight (Mn) of 974,000, a weight average molecular weight (Mw) of 1,315,000, and a molecular weight distribution (Mw / Mn) of 1.35 in GPC measurement. It was a thing.
  • the modified styrene butadiene rubber 5 had a styrene unit content of 22.1 mol% and a vinyl bond content in the butadiene unit of 60.0 mol%. Furthermore, when this modified styrene butadiene rubber 5 was subjected to 1 H-NMR measurement, it was confirmed that a dimethylsilanol group was introduced.
  • the modified styrene butadiene rubber 5 obtained above was used in the same manner as in Example 1, except that the rubber composition was prepared and the rubber cross-linked test piece was prepared. And evaluated in the same manner. The results are shown in Table 1.
  • the styrene butadiene rubber 6 had a styrene unit content of 21.1 mol% and a vinyl bond content in the butadiene unit of 58.8 mol%. Further, when 1 H-NMR measurement was performed on the styrene butadiene rubber 6, no dimethylsilanol group was introduced, and the styrene butadiene rubber 6 was an unmodified rubber.
  • the rubber composition was prepared and the test piece of the rubber cross-linked product was prepared in the same manner as in Example 1 except that the styrene butadiene rubber 6 obtained above was used. Performed and evaluated in the same manner. The results are shown in Table 1.
  • the modified styrene butadiene rubber 7 had a styrene unit content of 21.8 mol% and a vinyl bond content in the butadiene unit of 60.8 mol%. Furthermore, when this modified styrene butadiene rubber 7 was subjected to 1 H-NMR measurement, it was confirmed that a dimethylsilanol group was introduced.
  • a modified styrene butadiene rubber 8 was produced in the same manner as in Example 1 except that 0.011 part of dimethyldichlorosilane was not used.
  • the obtained modified styrene butadiene rubber 8 has a number average molecular weight (Mn) of 499,000, a weight average molecular weight (Mw) of 638,000, and a molecular weight distribution (Mw / Mn) of 1.28 in GPC measurement. there were.
  • the modified styrene butadiene rubber 8 had a styrene unit content of 21.4 mol% and a vinyl bond content in the butadiene unit of 61.1 mol%. Furthermore, when this modified styrene butadiene rubber 8 was subjected to 1 H-NMR measurement, it was confirmed that a dimethylsilanol group was introduced.
  • the modified styrene butadiene rubber 8 obtained above was used in the same manner as in Example 1 to prepare a rubber composition and to prepare a test piece of a crosslinked rubber product. And evaluated in the same manner. The results are shown in Table 1.
  • Styrene butadiene rubber 9 was produced in the same manner as in Example 1 except that 0.059 part of dimethyl (dimethylamino) chlorosilane was not used.
  • the obtained styrene-butadiene rubber 9 has a number average molecular weight (Mn) of 1,009,000, a weight average molecular weight (Mw) of 1,312,000, and a molecular weight distribution (Mw / Mn) of 1.30 in GPC measurement. It was a thing.
  • the modified styrene butadiene rubber 9 had a styrene unit content of 20.4 mol% and a vinyl bond content in the butadiene unit of 59.1 mol%.
  • the rubber composition was prepared and the test piece of the rubber cross-linked product was prepared in the same manner as in Example 1 except that the styrene butadiene rubber 9 obtained above was used. Performed and evaluated in the same manner. The results are shown in Table 1.
  • the modified styrene butadiene rubber 10 obtained above was used in the same manner as in Example 1 to prepare a rubber composition and prepare a test piece of a crosslinked rubber product. And evaluated in the same manner. The results are shown in Table 1.
  • the modified styrene butadiene rubber 11 obtained above was used in the same manner as in Example 1 to prepare a rubber composition and prepare a test piece of a crosslinked rubber product. And evaluated in the same manner. The results are shown in Table 1.
  • Example 7 A modified styrene-butadiene rubber 12 was produced in the same manner as in Example 1 except that tetrachlorosilane 0.014 was used instead of 0.011 part of dimethyldichlorosilane. Since the obtained modified styrene butadiene rubber 12 was gelled and insoluble in a solvent, GPC measurement and 1 H-NMR measurement were not possible.
  • the modified styrene butadiene rubber 12 obtained above was used in the same manner as in Example 1 to prepare a rubber composition and prepare a test piece of a rubber cross-linked product. And evaluated in the same manner. The results are shown in Table 1.
  • a modified styrene butadiene rubber 13 was produced in the same manner as in Example 1 except that 0.010 trimethylchlorosilane was used instead of 0.011 part of dimethyldichlorosilane.
  • the obtained modified styrene butadiene rubber 13 has a number average molecular weight (Mn) of 536,000, a weight average molecular weight (Mw) of 627,000, and a molecular weight distribution (Mw / Mn) of 1.17 in GPC measurement. there were.
  • the modified styrene butadiene rubber 13 had a styrene unit content of 20.3% mol% and a vinyl bond content in the butadiene unit of 58.9 mol%. Furthermore, when this modified styrene butadiene rubber 13 was subjected to 1 H-NMR measurement, it was confirmed that a dimethylsilanol group was introduced.
  • the modified styrene butadiene rubber 13 obtained above was used in the same manner as in Example 1 to prepare a rubber composition and to prepare a test piece of a crosslinked rubber product. And evaluated in the same manner. The results are shown in Table 1.
  • an alkali metalated aromatic compound having two carbon atoms directly bonded to an alkali metal atom and an aromatic ring in one molecule is used, and a bifunctional coupling agent is used.
  • the modified conjugated diene rubber obtained by the coupling reaction and the modification with a modifying agent having one atom or reactive group in one molecule capable of reacting with the active terminal is inhibited from gelation.
  • the rubber cross-linked product obtained by using this was excellent in low heat build-up and had high tensile strength (Examples 1 to 5).
  • the resulting rubber cross-linked product will be inferior in low heat build-up and tensile strength.
  • a monofunctional coupling agent is used as the ring agent, the molecular weight of the modified conjugated diene rubber is low, and the resulting rubber cross-linked product is inferior in low heat buildup and tensile strength (comparison). Examples 7 and 8).

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
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Abstract

L'invention concerne un procédé de production d'un caoutchouc à base de diène conjugué modifié, le procédé comprenant : une première étape, dans laquelle un composé aromatique contenant un métal alcalin ayant, dans la molécule, deux atomes de carbone chacun directement lié à la fois à un atome de métal alcalin et à l'anneau aromatique est utilisé en tant qu'initiateur de polymérisation pour polymériser un ou plusieurs monomères comprenant un composé diène conjugué, ce qui permet d'obtenir un caoutchouc à base de diène conjugué ayant une terminaison active ; une deuxième étape, dans laquelle le caoutchouc à base de diène conjugué ayant une terminaison active est soumis à une réaction de couplage à l'aide d'un agent de couplage bifonctionnel ; et une troisième étape, dans laquelle la terminaison active du caoutchouc à base de diène conjugué ayant subi la réaction de couplage est mise à réagir avec un modificateur ayant, dans la molécule, un atome ou un groupe réactif susceptible de réagir avec la terminaison active, ce qui permet d'obtenir un caoutchouc à base de diène conjugué modifié.
PCT/JP2018/012105 2017-03-31 2018-03-26 Procédé de production d'un caoutchouc à base de diène conjugué modifié WO2018181161A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3725368A (en) * 1970-01-19 1973-04-03 Lithium Corp Preparation of polymers
JP2009091498A (ja) * 2007-10-10 2009-04-30 Nippon Zeon Co Ltd 共役ジエン重合体組成物の製造方法
WO2014104169A1 (fr) * 2012-12-26 2014-07-03 日本ゼオン株式会社 Procédé pour la production de caoutchouc diénique conjugué modifié
JP2016530361A (ja) * 2013-07-22 2016-09-29 トリンゼオ ヨーロッパ ゲゼルシャフト ミット ベシュレンクテル ハフツング 重合反応開始剤
JP2017190400A (ja) * 2016-04-13 2017-10-19 デンカ株式会社 ビニル芳香族炭化水素系重合体、重合体組成物及び成形体

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3725368A (en) * 1970-01-19 1973-04-03 Lithium Corp Preparation of polymers
JP2009091498A (ja) * 2007-10-10 2009-04-30 Nippon Zeon Co Ltd 共役ジエン重合体組成物の製造方法
WO2014104169A1 (fr) * 2012-12-26 2014-07-03 日本ゼオン株式会社 Procédé pour la production de caoutchouc diénique conjugué modifié
JP2016530361A (ja) * 2013-07-22 2016-09-29 トリンゼオ ヨーロッパ ゲゼルシャフト ミット ベシュレンクテル ハフツング 重合反応開始剤
JP2017190400A (ja) * 2016-04-13 2017-10-19 デンカ株式会社 ビニル芳香族炭化水素系重合体、重合体組成物及び成形体

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