WO2016136889A1 - 変性共役ジエン系ゴムの製造方法 - Google Patents
変性共役ジエン系ゴムの製造方法 Download PDFInfo
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- WO2016136889A1 WO2016136889A1 PCT/JP2016/055662 JP2016055662W WO2016136889A1 WO 2016136889 A1 WO2016136889 A1 WO 2016136889A1 JP 2016055662 W JP2016055662 W JP 2016055662W WO 2016136889 A1 WO2016136889 A1 WO 2016136889A1
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- diene rubber
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- 0 *C1c2c(*)c(C3C(*)=C(*)C(*)=C(*)C33)c3c(*)c2C1* Chemical compound *C1c2c(*)c(C3C(*)=C(*)C(*)=C(*)C33)c3c(*)c2C1* 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C19/00—Chemical modification of rubber
- C08C19/30—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule
- C08C19/42—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule reacting with metals or metal-containing groups
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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
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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
- B60C11/00—Tyre tread bands; Tread patterns; Anti-skid inserts
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C19/00—Chemical modification of rubber
- C08C19/25—Incorporating silicon atoms into the molecule
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C19/00—Chemical modification of rubber
- C08C19/30—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule
- C08C19/32—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule reacting with halogens or halogen-containing groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C19/00—Chemical modification of rubber
- C08C19/30—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule
- C08C19/42—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule reacting with metals or metal-containing groups
- C08C19/44—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule reacting with metals or metal-containing groups of polymers containing metal atoms exclusively at one or both ends of the skeleton
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- 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
- C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F236/02—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
- C08F236/04—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
- C08F236/10—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 with vinyl-aromatic monomers
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- 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
-
- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/46—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides selected from alkali metals
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- 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
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/011—Crosslinking or vulcanising agents, e.g. accelerators
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- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
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- 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
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- 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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/15—Heterocyclic compounds having oxygen in the ring
- C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
- C08K5/1515—Three-membered rings
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- 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 specifically, a rubber cross-linked product having excellent workability and excellent tensile strength, elongation at break, low exothermic property, and wet grip properties can be provided.
- the present invention relates to a method for producing a modified conjugated diene rubber.
- 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.
- 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 includes at least a conjugated diene compound using, as a polymerization initiator, an alkali metalated aromatic compound having 3 or more carbon atoms bonded directly to an alkali metal atom and an aromatic ring in one molecule.
- a method for producing a radial conjugated diene polymer by polymerizing a monomer mixture is disclosed.
- the conjugated diene polymer has a radial structure, thereby improving the affinity with the filler when a filler such as silica is added. The wear resistance can be improved.
- the radial conjugated diene polymer is further improved in low exothermicity by using a modifying agent having an alkoxy group. If the point is not adjusted, there is a problem that gelation (three-dimensional cross-linking) occurs due to the modification reaction and the processability becomes inferior, and therefore further improvement has been desired.
- the present invention has been made in view of such a situation, and it is excellent in workability, and is capable of giving a rubber cross-linked product excellent in tensile strength, elongation at break, low exothermic property, and wet grip properties.
- An object is to provide a method for producing a conjugated diene rubber.
- the present inventor causes an alkali metal atom to react with an aromatic compound having three or more carbon atoms directly bonded to an aromatic ring as a polymerization initiator.
- an alkali metalated aromatic compound obtained by polymerizing a monomer comprising at least a conjugated diene compound, and reacting an active controller with the active terminal of the resulting conjugated diene rubber.
- a modified conjugated diene rubber can be obtained that is capable of providing a rubber cross-linked product having excellent workability and excellent tensile strength, elongation at break, low heat build-up, and wet grip.
- the present invention has been completed.
- the aromatic compound having 3 or more carbon atoms bonded directly to the aromatic ring in one molecule is preferably a compound represented by the following general formula (1).
- R 1 to R 8 are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and three or more of R 1 to R 8 have 1 And m is an integer of 0 to 5, and when m is 2 or more, 3 or more benzenes exist regardless of the structure represented by the general formula (1).
- the rings may be condensed with each other at an arbitrary position.
- the modifier is preferably a compound represented by the following general formula (2).
- X 1 is X 2 or R 11 X 2 (X 2 is a halogen atom, R 11 is an alkylene group having 1 to 4 carbon atoms), R 9 , R 10 is each independently an alkyl group having 1 to 10 carbon atoms, and n is an integer of 1 to 3.)
- the activity control agent is preferably a compound represented by the following general formula (3) and / or (4), more preferably ethylene oxide and / or propylene oxide.
- R 12 and R 13 are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.
- R 14 to R 17 are Each independently a hydrogen atom or an alkyl group having 1 to 12 carbon atoms.
- 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 providing a rubber cross-linked product having excellent workability and excellent tensile strength, elongation at break, low heat build-up property, and wet grip properties
- the modified conjugated diene It is possible to provide a rubber composition containing a rubber and a rubber crosslinked product obtained by using the rubber composition and excellent in tensile strength, elongation at break, low heat build-up property, and wet grip.
- a fourth step of reacting a modifying agent having an alkoxy group and a halogen atom-containing group to obtain a modified conjugated diene rubber.
- the first step in the production method of the present invention is a step of obtaining an alkali metalated aromatic compound by reacting an aromatic metal atom with an aromatic compound having 3 or more carbon atoms directly bonded to an aromatic ring in one molecule. It is.
- the alkali metalated aromatic compound obtained in the first step is used as a polymerization initiator in the second step described later.
- the aromatic ring constituting the aromatic compound having 3 or more carbon atoms directly bonded to the aromatic ring in the molecule is not particularly limited as long as it is a conjugated ring having aromaticity.
- Naphthalene rings, anthracene rings, and other electrically neutral aromatic hydrocarbon rings cyclopentadienyl anion rings, indenyl anion rings, fluorenyl anion rings, and other negatively charged aromatic hydrocarbon rings
- An aromatic ring containing a hetero atom such as a ring or a thiophene ring;
- an electrically neutral aromatic hydrocarbon ring is preferable, and a benzene ring is particularly preferable.
- Examples of the aromatic compound having three or more carbon atoms directly bonded to the aromatic ring in one molecule include the aromatic compound represented by the following general formula (1) and the following general formula (5).
- An aromatic compound represented by the following general formula (1) is preferable among them.
- R 1 to R 8 are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and three or more of R 1 to R 8 have 1 to 10 alkyl groups.
- m is an integer of 0 to 5, and when m is 2 or more, three or more benzene rings are condensed with each other at any position regardless of the structure represented by the general formula (1). It may be what you did.
- the above “independently” means that, for example, when m is 2 or more, there are a plurality of R 5 and R 8, but a plurality of R 5 or R 8 may be the same. , Meaning it may be different.
- m is 0, and three of R 1 , R 2 , R 3 , R 4 , R 6 , and R 7 are alkyl groups having 1 to 10 carbon atoms, R 1 , Of the R 2 , R 3 , R 4 , R 6 and R 7 , the remainder is preferably a hydrogen atom.
- R 18 to R 22 are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and one or more of R 18 to R 22 have 1 to 10 carbon atoms. It is an alkyl group.
- A represents an arbitrary linking group, and p is an integer of 3 to 100.
- the above “independently” means that, for example, when p is 3 or more, there are a plurality of R 18 to R 22, but there are a plurality of R 18 , R 19 , R 20 , R 21 , or R 22 also means that they may be the same or different.
- aromatic compound represented by the general formula (1) examples include 1,2,3-trimethylbenzene, 1,2,4-trimethylbenzene, 1,3,5-trimethylbenzene, hexamethylbenzene, 1,2,3-triethylbenzene, 1,2,4-triethylbenzene, 1,3,5-triethylbenzene, 1,2,3-tripropylbenzene, 1,2,4-tripropylbenzene, 1,3 Benzenes having three or more alkyl groups such as 1,3,5-tributylbenzene, 1,3,5-tripentylbenzene, 2,3,5-trimethylnaphthalene, And naphthalenes having three or more alkyl groups such as 4,5-trimethylnaphthalene.
- aromatic compound represented by the general formula (5) examples include o-methylstyrene oligomer, m-methylstyrene oligomer, p-methylstyrene oligomer, p-ethylstyrene oligomer, and p-propylstyrene oligomer.
- a styrene polymer in which one or more hydrogens on the benzene ring are substituted with an alkyl group such as p-butylstyrene oligomer and p-pentylstyrene oligomer.
- the alkali metal atom reacted with an aromatic compound having 3 or more carbon atoms directly bonded to the aromatic ring in the molecule is not particularly limited, but lithium, sodium, Or it is preferable that it is potassium, and lithium is especially preferable among these.
- the method of reacting an alkali metal atom with an aromatic compound having three or more carbon atoms directly bonded to an aromatic ring in a molecule is not particularly limited, but in an inert solvent under an inert atmosphere, A method of reacting an organic alkali metal compound is suitable.
- the organic alkali metal compound is not particularly limited, and an alkali metal compound having an alkyl group or an aryl group is preferably used. Specific examples thereof include methyl lithium, methyl sodium, methyl potassium, ethyl lithium, ethyl sodium, ethyl Potassium, n-propyl lithium, isopropyl potassium, n-butyl lithium, s-butyl lithium, t-butyl lithium, n-butyl sodium, n-butyl potassium, n-pentyl lithium, n-amyl lithium, n-octyl lithium, Examples include phenyl lithium, naphthyl lithium, phenyl sodium, and naphthyl sodium.
- an alkali metal compound having an alkyl group is preferable, a lithium compound having an alkyl group is more preferable, and n-butyllithium is particularly preferable.
- the amount of the organic alkali metal compound used for an aromatic compound having 3 or more carbon atoms directly bonded to the aromatic ring in the molecule is not particularly limited, 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 1.1 mol, per 1 mol of carbon atoms.
- alkyl (or aryl) potassium or alkyl (or aryl) sodium is used as the organic alkali metal compound
- a lithium compound having an alkyl group or an aryl group and a potassium or sodium compound having an alkoxy group are mixed.
- the potassium or sodium compound having an alkoxy group used at this time include t-butoxy potassium and t-butoxy sodium.
- the amount of the potassium or sodium compound having an alkoxy group is not particularly limited, but is usually 0.1 to 5.0 mol, preferably 0.2 to 3.0 mol based on the lithium compound having an alkyl group or an aryl group. Mol, more preferably 0.3 to 2.0 mol.
- the inert solvent is not particularly limited as long as it can dissolve the compound to be reacted, but a hydrocarbon solvent is preferably used.
- 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.
- reaction time and reaction temperature in the first step of the present invention 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 It is in the range of ⁇ 50 ° C. to 100 ° C.
- an organic alkali metal compound when it is reacted with an aromatic compound having 3 or more carbon atoms bonded directly to an aromatic ring in one molecule, it has a coordination ability to an alkali metal atom for the purpose of accelerating the reaction.
- a compound may coexist.
- a Lewis base compound containing a hetero atom is preferably used, and among these, a Lewis base compound containing a nitrogen atom or an oxygen atom is particularly preferably used. .
- Lewis base compounds containing nitrogen or oxygen atoms include chain ether compounds such as diethyl ether, anisole, diphenyl ether, dimethoxybenzene, dimethoxyethane, diglyme and ethylene glycol dibutyl ether; intramolecular such as trimethylamine and triethylamine Tertiary amine compounds having one nitrogen atom in them; Cyclic ether compounds having one oxygen atom in the molecule such as tetrahydrofuran and tetrahydropyran; Nitrogen-containing heterocyclic compounds such as pyridine, lutidine and 1-methylimidazole; Bistetrahydro Cyclic ether compounds having two or more oxygen atoms in the molecule such as furylpropane; N, N, N ′, N′-tetramethylethylenediamine, dipiperidinoethane, 1,4-diazabicyclo [2.2.2 Tertiary amine compounds having two or more nitrogen atoms in the molecule such as
- 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.
- a compound having a coordination ability to an alkali metal atom a compound having a relatively strong coordination ability, a cyclic ether compound having two or more oxygen atoms in the molecule, or two or more nitrogen atoms in the molecule
- the amount used is 1 mol of an alkali metal atom in an organic alkali metal compound to be reacted with an aromatic compound. In general, the range is 0.01 to 5 mol, preferably 0.01 to 2 mol, more preferably 0.01 to 1.5 mol.
- 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 reaction efficiency is improved when an organic alkali metal compound is reacted with an aromatic compound having three or more carbon atoms directly bonded to an aromatic ring in one molecule.
- a cyclic ether compound having two or more oxygen atoms in the molecule and a third having two or more nitrogen atoms in the molecule
- a range of 0.02 to 0.4 mol is particularly preferable with respect to 1 mol of a metal atom.
- each compound having the ability to coordinate to an alkali metal atom is allowed to coexist.
- the order of addition is not particularly limited. However, from the viewpoint of improving the generation efficiency of the alkali metalated aromatic compound, 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.
- an alkali metal atom is made to react with the aromatic compound which has 3 or more of carbon atoms directly bonded to the aromatic ring in 1 molecule.
- a metallized aromatic compound can be obtained.
- the alkali metalated aromatic compound is not particularly limited as long as it is a compound in which an alkali metal atom is bonded to an aromatic compound.
- usually an alkali metal atom and An alkali metalated aromatic compound having 3 or more carbon atoms directly bonded to the aromatic ring in one molecule can be obtained.
- the alkali metal atom in the alkali metalated aromatic compound, 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 them is usually present in an anionic state in order to bond to the alkali metal atom in such a cation state.
- the alkali metal atoms present in the cation state and the carbon atoms present in the anion state form an ionic bond, thereby directly bonding to each other. It has become a state.
- an alkali metalated aromatic compound having 3 or more carbon atoms directly bonded to the alkali metal atom and the aromatic ring in one molecule is obtained, and this is described in the second step.
- the conjugated diene polymer chain is used as a polymerization initiation point by using each of the carbon atoms directly bonded to three or more alkali metal atoms contained in the alkali metalated aromatic compound as a polymerization initiator. Since it grows with polymerization, the resulting conjugated diene rubber can have a radial structure.
- the aromatic compound represented by the above general formula (1) is used as an alkali metalated aromatic compound having 3 or more carbon atoms directly bonded to an alkali metal atom and an aromatic ring in one molecule.
- An alkali metalated aromatic compound represented by the following general formula (7), which is a group compound, can be exemplified.
- R 23 to R 30 are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, and an alkali metalation having 1 to 10 carbon atoms in which an alkali metal atom is bonded to the ⁇ -position. It represents any atom or group selected from alkyl groups, and three or more of R 23 to R 30 are alkali metalated alkyl groups having 1 to 10 carbon atoms in which an alkali metal atom is bonded to the ⁇ -position.
- M is an integer of 0 to 5, and when m is 2 or more, regardless of the structure represented by the general formula (6), three or more benzene rings are located at arbitrary positions with respect to each other. It may be condensed. Note that the above “independently” means that, for example, when m is 2 or more, there are a plurality of R 27 and R 30, but a plurality of R 27 or R 30 may also be the same. And it may be different.
- m is 0, and 3 of R 23 , R 24 , R 25 , R 26 , R 28 , and R 29 have 1 to 10 carbon atoms in which an alkali metal atom is bonded to the ⁇ -position. It is preferable that the remainder is a hydrogen atom among R ⁇ 23> , R ⁇ 24> , R ⁇ 25> , R ⁇ 26> , R ⁇ 28> , and R ⁇ 29 >.
- R 31 to R 35 are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, and an alkali metalation having 1 to 10 carbon atoms in which an alkali metal atom is bonded to the ⁇ -position. It represents any atom or group selected from alkyl groups, and at least one of R 31 to R 35 is an alkali metalated alkyl group having 1 to 10 carbon atoms in which an alkali metal atom is bonded to the ⁇ -position.
- A represents an arbitrary linking group, and p is an integer of 3 to 100.
- a monomer comprising at least a conjugated diene compound is polymerized using the alkali metalated aromatic compound obtained in the first step, and a conjugate having an active end.
- This is a process for obtaining a diene rubber.
- the alkali metalated aromatic compound obtained in the first step usually acts as a polymerization initiator.
- the conjugated diene compound is not particularly limited.
- 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 and the like 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 is optionally added to the conjugated diene compound and the aromatic vinyl compound in addition to the conjugated diene compound and 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 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 is excellent in 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 these compounds having the ability to coordinate to the alkali metal atom is usually 20 mol or less, preferably 15 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 5 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.
- a solution containing the compound may be used as it is. it can.
- a cyclic ether compound having two or more oxygen atoms in the molecule and a third having two or more nitrogen atoms in the molecule.
- An alkali metal compound using at least one compound selected from a tertiary 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 metal)
- the alkali metal compound here is an alkali metal
- gum which has moderate vinyl bond content is obtained, As a result, the rubber crosslinked material obtained using this can be made more excellent in low exothermic property.
- 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 inert in the polymerization reaction and can dissolve the monomer and the polymerization catalyst, but a hydrocarbon solvent is preferably used.
- a hydrocarbon solvent is preferably used.
- aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene
- aliphatic hydrocarbons such as n-hexane, n-heptane, and n-octane
- alicyclic rings such as cyclohexane, cyclopentane, and methylcyclohexane Group hydrocarbons
- ethers such as tetrahydrofuran, diethyl ether, cyclopentyl methyl ether; and the like.
- 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 second step, the conjugated diene rubber obtained by the polymerization reaction has an active end.
- an active control agent is reacted with the active end of the conjugated diene rubber obtained by the polymerization reaction, and then a specific modification is performed.
- a modified conjugated diene rubber is obtained by reacting an agent.
- the conjugated diene rubber having an active end obtained in the second step in the production method of the present invention uses the alkali metalated aromatic compound obtained in the first step described above, it is usually radial. It has the structure of. And, by having a radial structure, the number of active ends in one molecule is larger than that of a linear conjugated diene rubber in which only one side of the polymer chain is an active end, and it can be efficiently modified. As a result, the affinity with silica is further improved. Further, by having a radial structure, a multi-branched structure can be obtained without using a coupling agent.
- the third step is a conjugated diene rubber obtained by reacting an active control agent with the active end of the conjugated diene rubber having an active end obtained in the second step and reacting with the active control agent. It is the process of obtaining.
- the activity control agent is not particularly limited, and can react with the active end of the conjugated diene rubber having the active end obtained in the second step, and after the reaction, the activity of the active end is reduced. There is no particular limitation as long as it is a compound that can be used. In order to reduce the activity of the active end, in addition to directly reducing the activity of the active end itself, a structure that makes it difficult for the denaturant to react with the active end (for example, the denaturant is unlikely to approach the active end). It is also possible to provide such a structure.
- Examples of the activity control agent include a compound represented by the following general formula (3) or a compound represented by the following general formula (4).
- R 12 and R 13 are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, preferably a hydrogen atom.
- R 14 to R 17 are each independently a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and preferably R 14 , R 15 , and R 16 are hydrogen atoms.
- R 17 is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms.
- ethylene oxide and a propylene oxide are preferable and a propylene oxide is more preferable.
- the reaction in the third step proceeds according to the following reaction formula, and is represented by the following general formula (9).
- a conjugated diene rubber reacted with an activity control agent can be obtained.
- the conjugated diene rubber having an active end obtained in the second step is represented by the general formula (8).
- Polymer represents a base polymer constituting a conjugated diene rubber having an active terminal
- M 1 represents an alkali metal atom.
- the reaction in the third step proceeds according to the following reaction formula, and the following general formula (10) and / or A conjugated diene rubber reacted with an activity control agent represented by the following general formula (11) can be obtained.
- the conjugated diene rubber having an active end obtained in the second step is represented by the general formula (8).
- the amount of the activity control agent used in the third step of the production method of the present invention is not particularly limited, but is 0.05 to 5 per 1 mol of alkali metal atom in the alkali metalated aromatic compound used as the polymerization initiator.
- the amount is preferably in the range of mol, more preferably 0.1 to 3 mol, and particularly preferably 0.5 to 1.5 mol.
- an activity control agent may be used individually by 1 type, and may be used in combination of 2 or more type.
- the method of reacting the active control agent with the active end of the conjugated diene rubber having an active end obtained in the second step is not particularly limited, but the conjugated diene having an active end obtained in the second step is not limited.
- dissolve these are 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 method of adding the activity control agent to the conjugated diene rubber having an active end obtained in the above-described second step as it is in the polymerization solution used for the polymerization is 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 fourth step in the production method of the present invention will be described.
- the active terminal of the conjugated diene rubber reacted with the activity control agent obtained in the third step is reacted with a modifier having an alkoxy group and a halogen atom-containing group.
- a modified conjugated diene rubber is obtained.
- the conjugated diene rubber is modified by reacting an active end of the conjugated diene rubber reacted with the activity control agent with a modifier having an alkoxy group and a halogen atom-containing group.
- the resulting modified conjugated diene rubber is excellent in processability, and has a cross-linked rubber that is excellent in tensile strength, elongation at break, low heat build-up, and wet grip. Can be given.
- the halogen atom in the modifier reacts with the active end as one embodiment, so that the conjugated diene rubber
- An alkoxy group can be introduced at the end of the compound, and the alkoxy group is hydrolyzed as necessary to exhibit high affinity for a filler such as silica. And the effect
- action of such an alkoxy group can make the rubber crosslinked material obtained especially excellent in tensile strength, breaking elongation, low exothermic property, and wet grip property.
- the alkoxy group is highly reactive. Therefore, when the modifier containing the alkoxy group is reacted directly with the active end of the conjugated diene rubber having a radial structure, the alkoxy group is highly reactive. Due to the property, there is a problem that gelation (three-dimensional crosslinking) occurs.
- a step of reacting an active control agent with the active end of the conjugated diene rubber and reducing the activity of the active end of the conjugated diene rubber is adopted. is there.
- the conjugated diene rubber whose activity is reduced by reacting the activity control agent in this way is reacted with a modifier having an alkoxy group and a halogen atom-containing group.
- a modifier having an alkoxy group and a halogen atom-containing group can be introduced into the terminal of a conjugated diene rubber having a radial structure while suppressing the problem of gelation due to the high reactivity of the alkoxy group.
- the rubber cross-linked product obtained is made to have tensile strength, elongation at break, low heat build-up, and wet grip properties while realizing excellent processability by suppressing processability degradation due to gelation. It can be made particularly excellent.
- the modifier having an alkoxy group and a halogen atom-containing group is not particularly limited, and the activity of the conjugated diene rubber having an alkoxy group and a halogen atom-containing group and reacting with the activity control agent obtained in the third step.
- Any compound that can react with the terminal may be used, but a compound represented by the following general formula (2) can be preferably used.
- X 1 is represented by X 2 or R 11 X 2 (X 2 is a halogen atom, preferably a chlorine atom, and R 11 is an alkylene group having 1 to 4 carbon atoms).
- R 9 and R 10 are each independently an alkyl group having 1 to 10 carbon atoms.
- N is an integer of 1 to 3.
- the alkali metal atom 1 in the alkali metallized aromatic compound used as a polymerization initiator The amount of halogen atoms contained in the halogen atom-containing group per mole is preferably in an amount in the range of 0.05 to 5 mol, more preferably in an amount of 0.1 to 3 mol, An amount of 0.5 to 1.5 mol is particularly preferable.
- the modifier which has an alkoxy group and a halogen atom containing group may be used individually by 1 type, and may be used in combination of 2 or more type.
- a method of reacting a modifier having an alkoxy group and a halogen atom-containing group with the active terminal of the conjugated diene rubber reacted with the activity control agent obtained in the third step described above Although it is not particularly limited, the conjugated diene rubber reacted with the activity control agent obtained in the third step described above and the modifier having an alkoxy group and a halogen atom-containing group in a solvent capable of dissolving them. And a method of mixing.
- 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 terminal obtained in the second step described above is kept in the polymerization solution used for the polymerization, and with the activity control agent in the third step.
- a method in which the reaction is performed in the polymerization solution used in the second step and a modifier having an alkoxy group and a halogen atom-containing group is added to the polymerization solution as it is is simple and preferable.
- the reaction temperature in the fourth 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.
- an unreacted active terminal remains, an alcohol such as methanol, ethanol, isopropanol or the like It is preferable to deactivate the unreacted active terminal by adding a polymerization terminator such as water to the polymerization solution.
- 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. Examples of the extender oil include paraffinic, aromatic and naphthenic petroleum softeners, plant softeners, and fatty acids. When using a petroleum softener, it is preferable that the content of polycyclic aromatics extracted by the method of IP346 (the inspection method of THE INSTITUTE PETROLEUM in the UK) is less than 3%.
- 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 the rubber from the solution by, for example, reprecipitation, solvent removal under heating, solvent removal under reduced pressure, or solvent removal by steam (steam stripping). It can be separated and obtained from the reaction mixture by a normal operation during separation.
- an alkali metal atom is reacted with an aromatic compound having three or more carbon atoms directly bonded to an aromatic ring in one molecule, thereby producing an alkali metalated aromatic.
- a compound is obtained, and in the second step, the conjugated diene compound is polymerized using the alkali metalated aromatic compound. Therefore, since the conjugated diene polymer chain grows with living polymerizability, each of the carbon atoms to which 3 or more alkali metal atoms are directly bonded, usually contained in the alkali metalated aromatic compound, is grown, The resulting conjugated diene rubber can have a radial structure.
- an active control agent is reacted with the active end of the conjugated diene rubber having such a radial structure, and in the subsequent fourth step, an alkoxy group and a halogen atom-containing group are reacted.
- a modified conjugated diene rubber having a radial structure and having an alkoxy group at the terminal is obtained by reacting the modifying agent having the same.
- the modified conjugated diene rubber of the present invention thus obtained has a radial structure, and thus has an improved affinity with a filler and the like, and further modifies its active terminal.
- the activity of the active terminal is lowered by reacting with an activity control agent, followed by reaction with a modifier having an alkoxy group and a halogen atom-containing group. Therefore, according to the present invention, the occurrence of gelation (three-dimensional crosslinking) of the conjugated diene rubber during the modification reaction can be effectively prevented, and as a result, the processability can be improved. It is.
- the modified conjugated diene rubber obtained by the production method of the present invention has an alkoxy group introduced at the end of the polymer chain, the effect of the alkoxy group greatly increases the affinity with a filler or the like. This can improve the tensile strength, elongation at break, low heat build-up, and wet grip when a filler such as silica is blended to form a rubber cross-linked product. is there.
- the ratio of the radial conjugated diene rubber (that is, the conjugated diene rubber having three or more branches) in the modified conjugated diene rubber obtained by the production method of the present invention is not particularly limited, but is usually 10 to 100 weights. %, Preferably 20 to 100% by weight.
- the processability of the modified conjugated diene rubber can be further improved, and the affinity with a filler such as silica can be further increased. .
- the weight average molecular weight 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 3,000,000 as a value measured by gel permeation chromatography in terms of polystyrene.
- the range is preferably 10,000 to 2,000,000, more preferably 100,000 to 1,500,000.
- 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 1.1 to 5.0, particularly preferably 1.2 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 not particularly limited, but is usually in the range of 20 to 150, preferably 30 to 120.
- 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 obtained by the production method of the present invention is usually 1 to 80 mol%, preferably 5 to 75 mol%.
- the vinyl bond amount is within the above range, the obtained rubber cross-linked product becomes more excellent in low heat build-up.
- 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) 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, quinone dioximes, 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-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 obtained by the production method of the present invention preferably occupies 10 to 100% by weight, preferably 40 to 100% by weight of the rubber component in the rubber composition. Is particularly preferred.
- a rubber cross-linked product excellent in tensile strength, elongation at break, low heat build-up, and wet grip is obtained. be able to.
- 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 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, so that the tensile strength, elongation at break, low exothermic property, and It has excellent wet grip properties.
- the modified conjugated diene rubber obtained by the production method of the present invention reduces the activity of the active terminal by reacting with an activity control agent prior to modifying the active terminal, followed by the alkoxy group. And a modifier having a halogen atom-containing group are reacted, and the occurrence of gelation due to the addition of the modifier is effectively suppressed. Therefore, silica as a filler is added to the modified conjugated diene rubber.
- the dispersibility of silica is not lowered due to the influence of the gel content, and therefore, the rubber cross-linking of the present invention obtained by using the modified conjugated diene rubber obtained by the production method of the present invention.
- the product has a well-dispersed silica as a filler, and as a result, is particularly excellent in tensile strength, elongation at break, low heat build-up, and wet grip. That.
- the rubber cross-linked product of the present invention makes use of such characteristics, for example, in tires, materials for each part of the tire such as cap tread, base tread, carcass, sidewall, bead part; hose, belt, mat, anti-proof 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 tensile strength, elongation at break, low heat build-up, and wet grip properties, and therefore can be suitably used as a tire material, particularly a fuel-efficient tire material.
- 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: A product manufactured by Tosoh Corporation and having two trade names “GMH-HR-H” connected in series was used. Detector: differential refractometer (trade name “RI-8220” manufactured by Tosoh Corporation) Eluent: Tetrahydrofuran Column temperature: 40 ° C
- GC (Agilent Technology, product name “Agilent GC 6890NGC”)
- MS (manufactured by Agilent Technologies, trade name “Agilent MS 5973MSD”)
- a viscoelasticity measuring device (Rheometrix, product name “ARES”) is used for a test piece having a length of 50 mm, a width of 12.7 mm, and a thickness of 2 mm. Tan ⁇ at 60 ° C. was measured under the condition of a frequency of 10 Hz. About this characteristic, it showed with the index
- the ratio (molar ratio) of unsubstituted product: 1 substituted product: 2 substituted product: 3 substituted product was determined to be 3: 3: 27: 67, and the methyl group lithio of 1,3,5-trimethylbenzene was obtained.
- the conversion rate is 87%, and the average number of lithium atoms introduced into one molecule of 1,3,5-trimethylbenzene is 2.44.
- Example 1 [Production of Modified Styrene Butadiene Rubber 1] In a nitrogen atmosphere, an autoclave was charged with 800 parts of cyclohexane, 94.8 parts of 1,3-butadiene, 25.2 parts of styrene, and 0.185 parts of tetramethylethylenediamine, and then the polymerization initiator obtained in Production Example 1 0.812 parts of a solution of 1 (lithiated 1,3,5-trimethylbenzene) (the amount of tetramethylethylenediamine present in the reaction system is sufficient for lithiation of 1,3,5-trimethylbenzene). Polymerization was started at 60 ° C., with 2.0 moles per mole of n-butyllithium used.
- the polymerization reaction was continued for 60 minutes, and after confirming that the polymerization conversion was in the range of 95% to 100%, 0.051 part of propylene oxide (activity control agent) was added and allowed to react for 15 minutes. Further, 0.306 part of chloromethyltriisopropoxysilane (modifier) was added and reacted for 30 minutes, and then 0.064 part of methanol was added as a polymerization terminator to obtain a solution containing a polymer.
- propylene oxide activity control agent
- chloromethyltriisopropoxysilane modifier
- the obtained modified styrene butadiene rubber 1 is an elution component (peak area ratio 22.0%) having an Mn of 172,000, an Mw of 222,000, and a molecular weight distribution (Mw / Mn) of 1.29 in GPC measurement.
- the distribution (Mw / Mn) is composed of an elution component (peak area ratio 39.5%) of 1.05.
- Mn is 428,000, Mw is 599,000, and the molecular weight distribution (Mw / Mn) is 1.40.
- the modified styrene butadiene rubber 1 had a styrene content of 21.7 mol% and a vinyl bond content in the butadiene unit of 59.8 mol%. Further, when 1 H-NMR was measured for the modified styrene butadiene rubber 1, it was confirmed that a methyltriisopropoxysilane group was introduced. The gel weight fraction of this modified styrene butadiene rubber 1 was measured according to the method described above. The results are shown in Table 1.
- silica trade name “Zeosil 1165MP” manufactured by Rhodia
- 3 parts of zinc oxide 2 parts of stearic acid and anti-aging N-Phenyl-N '-(1,3-dimethylbutyl) -p-phenylenedian (Ouchi Shinsei Chemical Industry Co., Ltd.) , Was added trade name "Nocrac 6C") 2 parts, and further kneaded for 2.5 minutes to discharge the kneaded product from the mixer.
- the temperature of the kneaded product at the end of kneading was 150 ° C.
- the kneaded product was cooled to room temperature, kneaded again in a Brabender type mixer at 110 ° C. for 2 minutes, and then the kneaded product was discharged from the mixer. Next, with an open roll at 50 ° C., the obtained kneaded product, 1.5 parts of sulfur, N-cyclohexyl-2-benzothiazolylsulfenamide (trade name, manufactured by Ouchi Shinsei Chemical Industry Co., Ltd.) as a crosslinking accelerator After kneading 1.8 parts of “Noxeller CZ-G” and 1.5 parts of diphenylguanidine (trade name “Noxeller D” manufactured by Ouchi Shinsei Chemical Co., Ltd.) as a crosslinking accelerator, a sheet-like rubber is kneaded.
- the composition was removed. And the obtained rubber composition is press-crosslinked at 160 ° C. for 20 minutes to obtain a rubber cross-linked product, and the obtained rubber cross-linked product (test piece) has wet grip properties, low exothermic properties, and tensile strength. And the elongation at break was evaluated.
- Table 1 the evaluation results of wet grip properties, low exothermic properties, tensile strength, and elongation at break are shown as ratios when the results of Comparative Example 1 described later are set to 100, respectively.
- Example 2 [Production of modified styrene butadiene rubber 2] A modified styrene butadiene rubber 2 was produced in the same manner as in Example 1 except that 0.200 part of chloromethylisopropoxydimethylsilane was used instead of 0.306 part of chloromethyltriisopropoxysilane as a modifier. went. The obtained modified styrene-butadiene rubber 2 was an elution component (peak area ratio 14.4%) having an Mn of 151,000, Mw of 192,000, and a molecular weight distribution (Mw / Mn) of 1.27 in GPC measurement.
- elution component peak area ratio 14.4%
- Elution component (peak area ratio 17.3%) with Mn of 361,000, Mw of 374,000, molecular weight distribution (Mw / Mn), Mn of 742,000, Mw of 753,000, molecular weight Distribution (Mw / Mn) is composed of an elution component (peak area ratio 68.3%) having a Mn of 444,000, Mw of 641,000 as a whole, and a molecular weight distribution (Mw / Mn) of 1.01. 1.44. Moreover, it was confirmed by the multi-angle light scattering measurement that the degree of branching of the peak on the polymer side is high.
- the modified styrene butadiene rubber 2 had a styrene content of 22.4 mol% and a vinyl bond content in the butadiene unit of 60.1 mol%. Furthermore, when 1 H-NMR was measured for this modified styrene butadiene rubber 2, it was confirmed that a methylisopropoxydimethylsilane group was introduced. The gel weight fraction of this modified styrene butadiene rubber 2 was measured according to the method described above. The results are shown in Table 1.
- Example 1 a rubber composition and a rubber cross-linked product were obtained in the same manner as in Example 1 except that the modified styrene butadiene rubber 2 obtained above was used in place of the modified styrene butadiene rubber 1.
- Example 1 Evaluation was performed in the same manner as above. The results are shown in Table 1.
- Example 3 A modified styrene butadiene rubber 3 was produced in the same manner as in Example 1 except that 0.255 part of chloromethyltriethoxysilane was used instead of 0.306 part of chloromethyltriisopropoxysilane as a modifier. went.
- the obtained modified styrene butadiene rubber 3 is an elution component (peak area ratio 14.1%) having an Mn of 158,000, an Mw of 210,000, and a molecular weight distribution (Mw / Mn) of 1.33 in GPC measurement.
- Mn is 432,000, Mw is 619,000, and molecular weight distribution (Mw / Mn) is. It was 1.43. Moreover, it was confirmed by the multi-angle light scattering measurement that the degree of branching of the peak on the polymer side is high.
- the modified styrene butadiene rubber 3 had a styrene content of 21.5 mol% and a vinyl bond content in the butadiene unit of 60.3 mol%. Furthermore, when 1 H-NMR was measured for this modified styrene butadiene rubber 3, it was confirmed that a methyltriethoxysilane group was introduced. The gel weight fraction of this modified styrene butadiene rubber 3 was measured according to the method described above. The results are shown in Table 1.
- Example 1 a rubber composition and a rubber cross-linked product were obtained in the same manner as in Example 1 except that the modified styrene butadiene rubber 3 obtained above was used in place of the modified styrene butadiene rubber 1.
- Example 1 Evaluation was performed in the same manner as above. The results are shown in Table 1.
- Example 1 The polyorganosiloxane 0.260 represented by the following formula (12) was used instead of 0.306 parts of chloromethyltriisopropoxysilane as a modifying agent in that no reaction with propylene oxide as an activity control agent was performed.
- a modified styrene butadiene rubber 4 was produced in the same manner as in Example 1 except that the part was used in the state of a xylene solution having a concentration of 22%.
- the obtained modified styrene butadiene rubber 4 is an elution component (peak area ratio 15.5%) having an Mn of 166,000, an Mw of 207,000, and a molecular weight distribution (Mw / Mn) of 1.25 in GPC measurement, Elution component (peak area ratio 14.3%) with Mn of 377,000, Mw of 381,000, molecular weight distribution (Mw / Mn), and Mn of 726,000, Mw of 769,000, molecular weight Distribution (Mw / Mn) consists of 1.06 elution component (peak area ratio 70.2%), Mn is 438,000 as a whole, Mw is 626,000, and molecular weight distribution (Mw / Mn) is It was 1.43.
- the modified styrene butadiene rubber 4 had a styrene content of 21.5 mol% and a vinyl bond content in the butadiene unit of 59.6 mol%. Furthermore, when this modified styrene butadiene rubber 4 was measured for 1 H-NMR, it was confirmed that a siloxane group was introduced. The gel weight fraction of this modified styrene butadiene rubber 4 was measured according to the method described above. The results are shown in Table 1.
- Example 1 a rubber composition and a rubber cross-linked product were obtained in the same manner as in Example 1 except that the modified styrene butadiene rubber 4 obtained above was used instead of the modified styrene butadiene rubber 1.
- Example 1 Evaluation was performed in the same manner as above. The results are shown in Table 1.
- Example 2 A modified styrene butadiene rubber 5 was produced in the same manner as in Example 1 except that the reaction with propylene oxide as an activity control agent was not performed.
- the obtained modified styrene-butadiene rubber 5 was an elution component (peak area ratio 14.2%) having an Mn of 175,000, an Mw of 219,000, and a molecular weight distribution (Mw / Mn) of 1.25 in GPC measurement.
- Elution component peak area ratio 8.4% with Mn of 390,000, Mw of 394,000, molecular weight distribution (Mw / Mn), Mn of 773,000, Mw of 818,000, molecular weight distribution Elution component (Mw / Mn) of 1.06 (peak area ratio 51.6%), Mn of 1,810,000, Mw of 2,005,000, and molecular weight distribution (Mw / Mn) of 1.11
- the total amount of Mn was 545,000, Mw was 1,004,000, and the molecular weight distribution (Mw / Mn) was 1.84. .
- the modified styrene-butadiene rubber 5 had a styrene content of 21.9 mol% and a vinyl bond content in the butadiene unit of 62.0 mol%. Furthermore, when 1 H-NMR was measured for the modified styrene butadiene rubber 5, it was confirmed that a methyltriisopropoxysilane group was introduced. For this modified styrene butadiene rubber 5, the gel weight fraction was measured according to the method described above. The results are shown in Table 1.
- Example 1 a rubber composition and a rubber cross-linked product were obtained in the same manner as in Example 1 except that the modified styrene butadiene rubber 5 obtained above was used instead of the modified styrene butadiene rubber 1.
- Example 1 Evaluation was performed in the same manner as above. The results are shown in Table 1.
- the obtained modified styrene butadiene rubber 6 had a Mn of 209,000, a Mw of 215,000, and a molecular weight distribution (Mw / Mn) of 1.03 in GPC measurement.
- the modified styrene-butadiene rubber 6 had a styrene content of 21.4 mol% and a vinyl bond content in the butadiene unit of 59.9 mol%.
- 1 H-NMR was measured for this modified styrene butadiene rubber 6, it was confirmed that a methyltriisopropoxysilane group was introduced.
- the gel weight fraction was measured according to the method described above. The results are shown in Table 1.
- Example 1 a rubber composition and a rubber cross-linked product were obtained in the same manner as in Example 1 except that the modified styrene butadiene rubber 6 obtained above was used in place of the modified styrene butadiene rubber 1.
- Example 1 Evaluation was performed in the same manner as above. The results are shown in Table 1.
- a modified styrene butadiene rubber 7 was produced in the same manner as in Example 1 except that 0.087 part of trimethylchlorosilane was used instead of 0.306 part of chloromethyltriisopropoxysilane as a modifier.
- the obtained modified styrene butadiene rubber 7 is an elution component (peak area ratio 16.2%) having an Mn of 169,000, an Mw of 210,000, and a molecular weight distribution (Mw / Mn) of 1.24 in GPC measurement.
- Elution component peak area ratio 11.8% with Mn of 376,000, Mw of 380,000, molecular weight distribution (Mw / Mn), and Mn of 723,000, Mw of 764,000, molecular weight Distribution (Mw / Mn) consists of 1.06 elution component (peak area ratio 72.0%), Mn is 440,000, Mw is 629,000, and molecular weight distribution (Mw / Mn) is overall. It was 1.43. Moreover, it was confirmed by the multi-angle light scattering measurement that the degree of branching of the peak on the polymer side is high.
- the modified styrene-butadiene rubber 7 had a styrene content of 22.3 mol% and a vinyl bond content in the butadiene unit of 60.0 mol%. Furthermore, when 1 H-NMR was measured for the modified styrene butadiene rubber 7, it was confirmed that a trimethylsilane group was introduced. For this modified styrene butadiene rubber 7, the gel weight fraction was measured according to the method described above. The results are shown in Table 1.
- Example 1 a rubber composition and a rubber cross-linked product were obtained in the same manner as in Example 1 except that the modified styrene butadiene rubber 7 obtained above was used in place of the modified styrene butadiene rubber 1.
- Example 1 Evaluation was performed in the same manner as above. The results are shown in Table 1.
- Elution component (peak area ratio 14.6%) with Mn of 381,000, Mw of 386,000, molecular weight distribution (Mw / Mn), and Mn of 741,000, Mw of 784,000, molecular weight Distribution (Mw / Mn) consists of an elution component (peak area ratio 70.2%) of 1.06.
- Mn is 443,000
- Mw is 638,000
- molecular weight distribution (Mw / Mn) is 1.44.
- the modified styrene butadiene rubber 8 had a styrene content of 22.3 mol% and a vinyl bond content in the butadiene unit of 60.0 mol%. Furthermore, when 1 H-NMR was measured for this modified styrene butadiene rubber 8, it was confirmed that a tris (dimethylamino) silane group was introduced. For this modified styrene butadiene rubber 8, the gel weight fraction was measured according to the method described above. The results are shown in Table 1.
- Example 1 a rubber composition and a rubber cross-linked product were obtained in the same manner as in Example 1 except that the modified styrene butadiene rubber 8 obtained above was used instead of the modified styrene butadiene rubber 1, and Example 1 Evaluation was performed in the same manner as above. The results are shown in Table 1.
- an aromatic compound having 3 or more carbon atoms directly bonded to an aromatic ring in an molecule is reacted with an alkali metal atom to use an alkali metalated aromatic compound, and active.
- the activity control agent is reacted, and subsequently, the modifying agent having an alkoxy group and a halogen atom-containing group is reacted, the resulting modified conjugated diene rubber has a gel fraction.
- the rubber cross-linked product obtained using this was excellent in tensile strength, elongation at break, low heat build-up, and wet grip (Examples 1 to 3). .
- the resulting modified conjugated diene rubber has a high gel content, is inferior in processability, and further, when a rubber cross-linked product is used, The results were inferior in strength and elongation at break (Comparative Examples 1 and 2).
- n-butyllithium was used as a polymerization initiator, the resulting rubber cross-linked product was inferior in all of tensile strength, elongation at break, low exothermic property, and wet grip property (Comparative Example 3). ).
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Abstract
Description
さらに、本発明によれば、上記変性共役ジエン系ゴムを含むゴム成分100重量部に対して、シリカ10~200重量部を含有してなるゴム組成物が提供される。
本発明のゴム組成物は、架橋剤をさらに含有してなるものであることが好ましい。
本発明の変性共役ジエン系ゴムの製造方法は、芳香環に直接結合した炭素原子を1分子中に3個以上有する芳香族化合物に、アルカリ金属原子を反応させてアルカリ金属化芳香族化合物を得る第1工程と、前記アルカリ金属化芳香族化合物を用いて、少なくとも共役ジエン化合物を含んでなる単量体を重合し、活性末端を有する共役ジエン系ゴムを得る第2工程と、前記活性末端を有する共役ジエン系ゴムの活性末端に、活性制御剤を反応させて活性制御剤と反応した共役ジエン系ゴムを得る第3工程と、前記活性制御剤と反応した共役ジエン系ゴムの活性末端に、アルコキシ基およびハロゲン原子含有基を有する変性剤を反応させて、変性共役ジエン系ゴムを得る第4工程と、を備える。
まず、本発明の製造方法における、第1工程について説明する。本発明の製造方法における、第1工程は、芳香環に直接結合した炭素原子を1分子中に3個以上有する芳香族化合物に、アルカリ金属原子を反応させてアルカリ金属化芳香族化合物を得る工程である。なお、第1工程において得られるアルカリ金属化芳香族化合物は、後述する第2工程において、重合開始剤として用いられる。
次いで、本発明の製造方法における、第2工程について説明する。本発明の製造方法における、第2工程は、上記第1工程で得られたアルカリ金属化芳香族化合物を用いて、少なくとも共役ジエン化合物を含んでなる単量体を重合し、活性末端を有する共役ジエン系ゴムを得る工程である。なお、上記第1工程で得られたアルカリ金属化芳香族化合物は、通常、重合開始剤として作用する。
次いで、本発明の製造方法における、第3工程について説明する。本発明の製造方法における、第3工程は、上記第2工程で得られた活性末端を有する共役ジエン系ゴムの活性末端に、活性制御剤を反応させて活性制御剤と反応した共役ジエン系ゴムを得る工程である。
次いで、本発明の製造方法における、第4工程について説明する。本発明の製造方法における、第4工程は、上記第3工程で得られた活性制御剤と反応した共役ジエン系ゴムの活性末端に、アルコキシ基およびハロゲン原子含有基を有する変性剤を反応させて、変性共役ジエン系ゴムを得る工程である。
本発明のゴム組成物は、上述した本発明の製造方法により得られる変性共役ジエン系ゴムを含むゴム成分100重量部に対して、シリカ10~200重量部を含有してなる組成物である。
本発明のゴム架橋物は、上述した本発明のゴム組成物を架橋してなるものである。
本発明のゴム架橋物は、本発明のゴム組成物を用い、たとえば、所望の形状に対応した成形機、たとえば、押出機、射出成形機、圧縮機、ロールなどにより成形を行い、加熱することにより架橋反応を行い、架橋物として形状を固定化することにより製造することができる。この場合においては、予め成形した後に架橋しても、成形と同時に架橋を行ってもよい。成形温度は、通常、10~200℃、好ましくは25~120℃である。架橋温度は、通常、100~200℃、好ましくは130~190℃であり、架橋時間は、通常、1分~24時間、好ましくは2分~12時間、特に好ましくは3分~6時間である。
ゴムの分子量は、ゲルパーミエーションクロマトグラフィによりポリスチレン換算分子量として求めた。具体的な測定条件は、以下のとおりとした。
測定器:高速液体クロマトグラフ(東ソー社製、商品名「HLC-8220」)
カラム:東ソー社製、商品名「GMH-HR-H」を二本直列に連結したものを用いた。
検出器:示差屈折計(東ソー社製、商品名「RI-8220」)
溶離液:テトラヒドロフラン
カラム温度:40℃
ゴムの分岐度は、多角度光散乱光度計により測定した。具体的な測定条件は、以下のとおりとした。
ポンプ:Waters社製、商品名「MODEL515」
カラム:東ソー社製、商品名「GMH-HR-M」を三本直列に連結したものを用いた。
検出器:示差屈折計(Waters社製、商品名「RI-2414」)
検出器:多角度光散乱光度計(Wyatt Technology社製、商品名「DAWN EOS」)
溶離液:テトラヒドロフラン
カラム温度:23℃
1H-NMRにより測定した。
測定器:(JEOL社製、商品名「JNM-ECA-400WB」
測定溶媒:重クロロホルム
GC-MSにより測定した。
GC:(アジレント・テクノロジー社製、商品名「Agilent GC 6890NGC」)
MS:(アジレント・テクノロジー社製、商品名「Agilent MS 5973MSD」)
カラム:(アジレント・テクノロジー社製、商品名「DB1701」)
#100メッシュカゴにゴム(重量:Wa[g])を1mm角程度に裁断して入れ、トルエン中に室温(25℃)で24時間保管し、引き上げた。次いで、#100メッシュカゴに残ったゴムを真空乾燥して乾燥後の重量(Wb[g])を秤量した。そして、これらの秤量値から、ゲル重量分率を、トルエン不溶分=(Wb/Wa)×100(%)により求めた。なお、ゲル重量分率が低いほど、加工性に優れるものと判断することができる。
ウエットグリップ性については、長さ50mm、幅12.7mm、厚さ2mmの試験片について、粘弾性測定装置(レオメトリックス社製、製品名「ARES」)を用い、動的歪み0.5%、周波数10Hzの条件で0℃におけるtanδを測定した。この特性については、比較例1の測定値を100とする指数で示した。この指数が大きいものほど、ウエットグリップ性に優れる。
低発熱性については、長さ50mm、幅12.7mm、厚さ2mmの試験片について、粘弾性測定装置(レオメトリックス社製、製品名「ARES」)を用い、動的歪み2.5%、周波数10Hzの条件で60℃におけるtanδを測定した。この特性については、比較例1の測定値を100とする指数で示した。この指数が小さいものほど、低発熱性に優れる。
JISK6251に従って、ダンベル状3号形試験片を用いて引張試験を行ない、引張強度、破断伸びを測定した。この特性については、比較例1の測定値を100とする指数で示した。この指数が大きいものほど、引張強度、および破断伸びに優れる。
窒素雰囲気下、ガラス反応容器に、シクロヘキサン16部、1,3,5-トリメチルベンゼン0.841部、およびテトラメチルエチレンジアミン0.813部を加えた。次に攪拌しながら、n-ブチルリチウム1.345部(n-ブチルリチウム1モル当たり前記テトラメチルエチレンジアミン0.3モルとなる)を加え、反応温度60℃にて2日間静置ことで反応させ、重合開始剤1の溶液(リチオ化された1,3,5-トリメチルベンゼン)18.999部を得た。次に、反応により得られたリチオ化された1,3,5-トリメチルベンゼンのリチオ化率を測定する目的で、トリメチルシリルクロライドを過剰量加えたガラス容器に、得られた反応液を数滴加え、30分間反応させた。水道水にて触媒残渣を抽出洗浄した後に溶媒を留去することで、黄色いオイル状の液体を得た。
EI-MS,m/z=120(M+)(3%),m/z=192(M+)(3%),m/z=264(M+)(24%),m/z=336(M+)(70%)。Mw=120(3%)、Mw=192(3%)、Mw=264(24%)、Mw=336(70%)。
1H-NMR(CDCl3) 6.83(s,3H,Ph-H),6.73(s,1H,Ph-H),6.64(s,2H,Ph-H),6.55(s,2H,Ph-H),6.47(s,1H,Ph-H),6.39(s,3H,Ph-H),2.30(s,9H,Ph-CH3),2.28(s,6H,Ph-CH3),2.02(s,2H,Ph-CH2-SiMe3),2.26(s,3H,Ph-CH3),2.00(s,4H,Ph-CH2-SiMe3),1.98(s,6H,Ph-CH2-SiMe3)。
無置換体(1,3,5-トリメチルベンゼン)1H-NMR(CDCl3):6.83(s,3H,Ph-H),2.30(s,9H,Ph-CH3)、1置換体(1-トリメチルシリルメチル-3,5-ジメチルベンゼン)1H-NMR(CDCl3):6.73(s,1H,Ph-H),6.64(s,2H,Ph-H),2.28(s,6H,Ph-CH3),2.02(s,2H,Ph-CH2-SiMe3)、2置換体(1,3-ビス(トリメチルシリルメチル)-5-メチルベンゼン)1H-NMR(CDCl3):6.55(s,2H,Ph-H),6.47(s,1H,Ph-H),2.26(s,3H,Ph-CH3),2.00(s,4H,Ph-CH2-SiMe3)、3置換体(1,3,5-トリス(トリメチルシリルメチル)ベンゼン)1H-NMR(CDCl3):6.39(s,3H,Ph-H),1.98(s,6H,Ph-CH2-SiMe3)
〔変性スチレンブタジエンゴム1の製造〕
窒素雰囲気下、オートクレーブに、シクロヘキサン800部、1,3-ブタジエン94.8部、スチレン25.2部、およびテトラメチルエチレンジアミン0.185部を仕込んだ後、製造例1で得られた重合開始剤1の溶液(リチオ化された1,3,5-トリメチルベンゼン)0.812部を添加し(反応系中に存在するテトラメチルエチレンジアミンの量は、1,3,5-トリメチルベンゼンのリチオ化に用いたn-ブチルリチウム1モル当たり2.0モルである)、60℃で重合を開始した。60分間重合反応を継続し、重合転化率が95%から100%の範囲になったことを確認してから、酸化プロピレン(活性制御剤)0.051部を添加し、15分間反応させた。さらに、クロロメチルトリイソプロポキシシラン(変性剤)0.306部を添加し、30分間反応させた後、重合停止剤としてメタノール0.064部を添加して重合体を含有する溶液を得た。
次に、容量250mlのブラベンダータイプミキサー中で、上記にて得られた変性スチレンブタジエンゴム1 100部を30秒素練りし、次いでシリカ(ローディア社製、商品名「Zeosil1165MP」)50部、プロセスオイル(新日本石油社製、商品名「アロマックス T-DAE」)25部、およびシランカップリング剤:ビス(3-(トリエトキシシリル)プロピル)テトラスルフィド(デグッサ社製、商品名「Si69」)5.6部を添加して、110℃を開始温度として1.5分間混練後、シリカ(ローディア社製、商品名「Zeosil1165MP」)20部、酸化亜鉛3部、ステアリン酸2部および老化防止剤としてのN-フェニル-N’-(1,3-ジメチルブチル)-p-フェニレンジアン(大内新興化学工業社製、商品名「ノクラック6C」)2部を添加し、さらに2.5分間混練し、ミキサーから混練物を排出させた。混練終了時の混練物の温度は150℃であった。そして、混練物を、室温まで冷却した後、再度ブラベンダータイプミキサー中で、110℃を開始温度として2分間混練した後、ミキサーから混練物を排出させた。次いで、50℃のオープンロールで、得られた混練物と、硫黄1.5部、架橋促進剤としてのN-シクロヘキシル-2-ベンゾチアゾリルスルフェンアミド(大内新興化学工業社製、商品名「ノクセラーCZ-G」)1.8部、および同じく架橋促進剤としてのジフェニルグアニジン(大内新興化学工業社製、商品名「ノクセラーD」)1.5部を混練した後、シート状のゴム組成物を取り出した。そして、得られたゴム組成物を、160℃で20分間プレス架橋することで、ゴム架橋物を得て、得られたゴム架橋物(試験片)について、ウエットグリップ性、低発熱性、引張強度および破断伸びの評価を行なった。結果を表1に示す。なお、表1中においては、ウエットグリップ性、低発熱性、引張強度および破断伸びの評価結果は、後述する比較例1の結果を、それぞれ100とした場合における比率で示した。
〔変性スチレンブタジエンゴム2の製造〕
変性剤として、クロロメチルトリイソプロポキシシラン0.306部の代わりに、クロロメチルイソプロポキシジメチルシラン0.200部を使用した以外は、実施例1と同様にして、変性スチレンブタジエンゴム2の製造を行った。得られた変性スチレンブタジエンゴム2は、GPC測定において、Mnが151,000、Mwが192,000、分子量分布(Mw/Mn)が1.27の溶出成分(ピーク面積比14.4%)、Mnが361,000、Mwが374,000、分子量分布(Mw/Mn)が1.03の溶出成分(ピーク面積比17.3%)、およびMnが742,000、Mwが753,000、分子量分布(Mw/Mn)が1.01の溶出成分(ピーク面積比68.3%)からなるものであり、全体としてMnが444,000、Mwが641,000、分子量分布(Mw/Mn)が1.44のものであった。また、多角度光散乱測定により、高分子側のピークの分岐度が高い事が確認された。また、この変性スチレンブタジエンゴム2のスチレン含有量は22.4モル%、ブタジエン単位中のビニル結合含有量は60.1モル%であった。さらに、この変性スチレンブタジエンゴム2について、1H-NMRを測定したところ、メチルイソプロポキシジメチルシラン基が導入されていることが確認された。この変性スチレンブタジエンゴム2について、上記した方法にしたがい、ゲル重量分率を測定した。結果を表1に示す。
変性剤として、クロロメチルトリイソプロポキシシラン0.306部の代わりに、クロロメチルトリエトキシシラン0.255部を用いたこと以外は、実施例1と同様にして、変性スチレンブタジエンゴム3の製造を行った。得られた変性スチレンブタジエンゴム3は、GPC測定において、Mnが158,000、Mwが210,000、分子量分布(Mw/Mn)が1.33の溶出成分(ピーク面積比14.1%)、Mnが394,000、Mwが398,000、分子量分布(Mw/Mn)が1.01の溶出成分(ピーク面積比15.9%)、およびMnが738,000、Mwが783,000、分子量分布(Mw/Mn)が1.06の溶出成分(ピーク面積比70.0%)からなるものであり、全体としてMnが432,000、Mwが619,000、分子量分布(Mw/Mn)が1.43のものであった。また、多角度光散乱測定により、高分子側のピークの分岐度が高い事が確認された。また、この変性スチレンブタジエンゴム3のスチレン含有量は21.5モル%、ブタジエン単位中のビニル結合含有量は60.3モル%であった。さらに、この変性スチレンブタジエンゴム3について、1H-NMRを測定したところ、メチルトリエトキシシラン基が導入されていることが確認された。この変性スチレンブタジエンゴム3について、上記した方法にしたがい、ゲル重量分率を測定した。結果を表1に示す。
活性制御剤としての酸化プロピレンによる反応を行わなかった点、および、変性剤として、クロロメチルトリイソプロポキシシラン0.306部の代わりに、下記式(12)で表されるポリオルガノシロキサン0.260部を濃度22%のキシレン溶液の状態で使用した点以外は、実施例1と同様にして、変性スチレンブタジエンゴム4の製造を行った。得られた変性スチレンブタジエンゴム4は、GPC測定において、Mnが166,000、Mwが207,000、分子量分布(Mw/Mn)が1.25の溶出成分(ピーク面積比15.5%)、Mnが377,000、Mwが381,000、分子量分布(Mw/Mn)が1.01の溶出成分(ピーク面積比14.3%)、およびMnが726,000、Mwが769,000、分子量分布(Mw/Mn)が1.06の溶出成分(ピーク面積比70.2%)からなるものであり、全体としてMnが438,000、Mwが626,000、分子量分布(Mw/Mn)が1.43のものであった。また、多角度光散乱測定により、高分子側のピークの分岐度が高い事が確認された。また、この変性スチレンブタジエンゴム4のスチレン含有量は21.5モル%、ブタジエン単位中のビニル結合含有量は59.6モル%であった。さらに、この変性スチレンブタジエンゴム4について、1H-NMRを測定したところ、シロキサン基が導入されていることが確認された。この変性スチレンブタジエンゴム4について、上記した方法にしたがい、ゲル重量分率を測定した。結果を表1に示す。
活性制御剤としての酸化プロピレンによる反応を行わなかったこと以外は、実施例1と同様にして、変性スチレンブタジエンゴム5の製造を行った。得られた変性スチレンブタジエンゴム5は、GPC測定において、Mnが175,000、Mwが219,000、分子量分布(Mw/Mn)が1.25の溶出成分(ピーク面積比14.2%)、Mnが390,000、Mwが394,000、分子量分布(Mw/Mn)が1.01の溶出成分(ピーク面積比8.4%)、Mnが773,000、Mwが818,000、分子量分布(Mw/Mn)が1.06の溶出成分(ピーク面積比51.6%)、およびMnが1,810,000、Mwが2,005,000、分子量分布(Mw/Mn)が1.11の溶出成分(ピーク面積比25.8%)からなるものであり、全体としてMnが545,000、Mwが1,004,000、分子量分布(Mw/Mn)が1.84のものであった。また、多角度光散乱測定により、高分子側のピークの分岐度が高い事が確認された。また、この変性スチレンブタジエンゴム5のスチレン含有量は21.9モル%、ブタジエン単位中のビニル結合含有量は62.0モル%であった。さらに、この変性スチレンブタジエンゴム5について、1H-NMRを測定したところ、メチルトリイソプロポキシシラン基が導入されていることが確認された。この変性スチレンブタジエンゴム5について、上記した方法にしたがい、ゲル重量分率を測定した。結果を表1に示す。
窒素雰囲気下、オートクレーブに、シクロヘキサン800部、1,3-ブタジエン94.8部、スチレン25.2部、およびテトラメチルエチレンジアミン0.232部を仕込んだ後、n-ブチルリチウム0.051部を添加し、60℃で重合を開始した。60分間重合反応を継続し、重合転化率が95%から100%の範囲になったことを確認してから、酸化プロピレン(活性制御剤)0.051部を添加し、15分間反応させた。さらに、クロロメチルトリイソプロポキシシラン(変性剤)0.306部を添加し、30分間反応させた後、重合停止剤としてメタノール0.064部を添加して重合体を含有する溶液を得た。そして、重合体成分100部に対して、老化防止剤として2,4-ビス[(オクチルチオ)メチル]-o-クレゾール(チバスペシャルティケミカルズ社製、商品名「イルガノックス1520」)0.15部を溶液に添加した後、スチームストリッピングにより、溶媒を除去し、60℃で24時間真空乾燥して、固形状の変性スチレンブタジエンゴム6を得た。得られた変性スチレンブタジエンゴム6は、GPC測定において、Mnが209,000、Mwが215,000、分子量分布(Mw/Mn)が1.03のものであった。また、この変性スチレンブタジエンゴム6のスチレン含有量は21.4モル%、ブタジエン単位中のビニル結合含有量は59.9モル%であった。さらに、この変性スチレンブタジエンゴム6について、1H-NMRを測定したところ、メチルトリイソプロポキシシラン基が導入されていることが確認された。この変性スチレンブタジエンゴム6について、上記した方法にしたがい、ゲル重量分率を測定した。結果を表1に示す。
変性剤として、クロロメチルトリイソプロポキシシラン0.306部の代わりに、トリメチルクロロシラン0.087部を使用した以外は、実施例1と同様にして、変性スチレンブタジエンゴム7の製造を行った。得られた変性スチレンブタジエンゴム7は、GPC測定において、Mnが169,000、Mwが210,000、分子量分布(Mw/Mn)が1.24の溶出成分(ピーク面積比16.2%)、Mnが376,000、Mwが380,000、分子量分布(Mw/Mn)が1.01の溶出成分(ピーク面積比11.8%)、およびMnが723,000、Mwが764,000、分子量分布(Mw/Mn)が1.06の溶出成分(ピーク面積比72.0%)からなるものであり、全体としてMnが440,000、Mwが629,000、分子量分布(Mw/Mn)が1.43のものであった。また、多角度光散乱測定により、高分子側のピークの分岐度が高い事が確認された。また、この変性スチレンブタジエンゴム7のスチレン含有量は22.3モル%、ブタジエン単位中のビニル結合含有量は60.0モル%であった。さらに、この変性スチレンブタジエンゴム7について、1H-NMRを測定したところ、トリメチルシラン基が導入されていることが確認された。この変性スチレンブタジエンゴム7について、上記した方法にしたがい、ゲル重量分率を測定した。結果を表1に示す。
活性制御剤としての酸化プロピレンによる反応を行わなかった点、および、変性剤として、クロロメチルトリイソプロポキシシラン0.306部の代わりに、トリス(ジメチルアミノ)クロロシラン0.157部を使用した点以外は、実施例1と同様にして、変性スチレンブタジエンゴム8の製造を行った。得られた変性スチレンブタジエンゴム8は、GPC測定において、Mnが164,000、Mwが207,000、分子量分布(Mw/Mn)が1.27の溶出成分(ピーク面積比15.2%)、Mnが381,000、Mwが386,000、分子量分布(Mw/Mn)が1.01の溶出成分(ピーク面積比14.6%)、およびMnが741,000、Mwが784,000、分子量分布(Mw/Mn)が1.06の溶出成分(ピーク面積比70.2%)からなるものであり、全体としてMnが443,000、Mwが638,000、分子量分布(Mw/Mn)が1.44のものであった。また、多角度光散乱測定により、高分子側のピークの分岐度が高い事が確認された。また、この変性スチレンブタジエンゴム8のスチレン含有量は22.3モル%、ブタジエン単位中のビニル結合含有量は60.0モル%であった。さらに、この変性スチレンブタジエンゴム8について、1H-NMRを測定したところ、トリス(ジメチルアミノ)シラン基が導入されていることが確認された。この変性スチレンブタジエンゴム8について、上記した方法にしたがい、ゲル重量分率を測定した。結果を表1に示す。
重合開始剤として、n-ブチルリチウムを用いた場合には、得られるゴム架橋物は、引張強度、破断伸び、低発熱性、およびウエットグリップ性のいずれにも劣るものであった(比較例3)。
また、活性末端を変性するに変性するに先立って、活性制御剤を反応させたものの、アルコキシ基を含有しない変性剤を用いて変性を行った場合には、得られるゴム架橋物は、引張強度、破断伸び、およびウエットグリップ性に劣るものであった(比較例4)。
さらに、変性剤として、アミノ基を含有する変性剤を用いて変性を行った場合には、得られるゴム架橋物は、ウエットグリップ性が充分でなく、さらには、引張強度、および破断伸びに劣るものであった(比較例5)。
Claims (10)
- 芳香環に直接結合した炭素原子を1分子中に3個以上有する芳香族化合物に、アルカリ金属原子を反応させてアルカリ金属化芳香族化合物を得る第1工程と、
前記アルカリ金属化芳香族化合物を用いて、少なくとも共役ジエン化合物を含んでなる単量体を重合し、活性末端を有する共役ジエン系ゴムを得る第2工程と、
前記活性末端を有する共役ジエン系ゴムの活性末端に、活性制御剤を反応させて活性制御剤と反応した共役ジエン系ゴムを得る第3工程と、
前記活性制御剤と反応した共役ジエン系ゴムの活性末端に、アルコキシ基およびハロゲン原子含有基を有する変性剤を反応させて、変性共役ジエン系ゴムを得る第4工程と、を備える変性共役ジエン系ゴムの製造方法。 - 前記活性制御剤が、酸化エチレンおよび/または酸化プロピレンである請求項4に記載の変性共役ジエン系ゴムの製造方法。
- 請求項1~5のいずれかに記載の製造方法により得られる変性共役ジエン系ゴム。
- 請求項6に記載の変性共役ジエン系ゴムを含むゴム成分100重量部に対して、シリカ10~200重量部を含有してなるゴム組成物。
- 架橋剤をさらに含有してなる請求項7に記載のゴム組成物。
- 請求項8に記載のゴム組成物を架橋してなるゴム架橋物。
- 請求項9に記載のゴム架橋物を含んでなるタイヤ。
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CN107207632A (zh) | 2017-09-26 |
EP3263605B1 (en) | 2019-11-13 |
EP3263605A4 (en) | 2018-12-05 |
EP3263605A1 (en) | 2018-01-03 |
KR20170120113A (ko) | 2017-10-30 |
JP6607248B2 (ja) | 2019-11-20 |
US10414835B2 (en) | 2019-09-17 |
CN107207632B (zh) | 2020-04-14 |
US20180016362A1 (en) | 2018-01-18 |
JPWO2016136889A1 (ja) | 2017-12-07 |
KR102435190B1 (ko) | 2022-08-22 |
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