JP2020026494A - Acid-modified conjugated diene polymer composition and method for producing acid-modified conjugated diene polymer composition - Google Patents

Abstract

To provide a method for producing an acid-modified conjugated diene polymer composition having excellent cold flow resistance, and an acid-modified conjugated diene polymer composition.SOLUTION: A method for producing an acid-modified conjugated diene polymer composition has a step (1) in which a mixture of a modified conjugated diene polymer having a silicon atom in the structure and an organic acid is heated for at least 45 min. at 55°C or higher, or a step (2) in which such a mixture is kneaded at 100°C or higher, wherein, when the acid-modified conjugated diene polymer composition is stored at 50°C for two weeks, and a change width of Mooney viscosity at 100°C is 10 or less.SELECTED DRAWING: None

Description

  The present invention relates to an acid-modified conjugated diene-based polymer composition and a method for producing an acid-modified conjugated diene-based polymer composition.

  As a polymer composition for an automobile tire, a composition containing a conjugated diene-based polymer such as a conjugated diene-based elastomer polybutadiene or a styrene-butadiene copolymer has been used. When such a polymer composition is stored, a phenomenon called “cold flow” may occur in which the shape of the polymer composition collapses with the passage of time. For example, Patent Literature 1 studies reducing the cold flow by using a specific elastomer composition.

  It is known that a modified conjugated diene-based polymer having a hydrolyzable group such as an alkoxysilyl group changes its molecular weight over time, and that its viscosity increases over time. For example, Patent Literatures 2 and 3 consider suppressing the change with time of the molecular weight distribution of the modified conjugated diene-based polymer.

JP-A-11-20954 JP 2012-201863 A JP-T-2003-514960

  A polymer composition containing a modified conjugated diene-based polymer having a silicon atom in its structure is required to suppress a change in viscosity over time during storage and to further improve cold flow. An object of the present invention is to provide a method for producing an acid-modified conjugated diene-based polymer composition having excellent cold flow resistance, which suppresses the time-dependent change in viscosity during storage, and to provide an acid-modified conjugated diene-based polymer composition. And

  The present invention provides (1) a step of heat-treating a mixture of a modified conjugated diene-based polymer having a silicon atom in the structure and an organic acid at a temperature of 55 ° C or more for 45 minutes or more, or (2) a temperature of 100 ° C or more. A method for producing an acid-modified conjugated diene-based polymer composition comprising a step of kneading at a temperature of 100 ° C., wherein the acid-modified conjugated diene-based polymer composition is stored at 50 ° C. for 2 weeks and has a Mooney viscosity ML at 100 ° C. ( 1 + 4) A method in which a change width at 100 ° C. is 10 or less.

  The present invention also includes an acid-modified conjugated diene-based polymer having a silicon atom in the structure and a compound derived from an organic acid, and has a Mooney viscosity ML (1 + 4) at 100 ° C when stored at 50 ° C for 2 weeks of 100 ° C. The acid-modified conjugated diene-based polymer composition has a variation width of 10 or less.

  According to the present invention, it is possible to provide a method for producing an acid-modified conjugated diene-based polymer composition having excellent cold flow resistance, and an acid-modified conjugated diene-based polymer composition.

  This embodiment will be described in detail. Note that the present invention is not limited to the following embodiments.

  In the present specification, a hydrocarbyl group represents a monovalent group obtained by removing one hydrogen atom from a hydrocarbon. The hydrocarbylene group represents a divalent group obtained by removing two hydrogen atoms from a hydrocarbon. The hydrocarbyloxy group represents a monovalent group having a structure in which a hydrogen atom of a hydroxy group is replaced with a hydrocarbyl group. An amino group having a substituent (hereinafter sometimes referred to as a substituted amino group) has a structure in which at least one hydrogen atom of an amino group is replaced with a monovalent atom or a monovalent group other than a hydrogen atom. Or a group having a structure in which two hydrogen atoms of an amino group are replaced with a divalent group. The hydrocarbyl group having a substituent (hereinafter, sometimes referred to as a substituted hydrocarbyl group) represents a monovalent group having a structure in which at least one hydrogen atom of the hydrocarbyl group has been replaced with a substituent. A hydrocarbylene group having a nitrogen atom and / or an oxygen atom means that a carbon atom and / or a hydrogen atom other than the carbon atom from which the hydrogen atom of the hydrocarbylene group is removed has a nitrogen atom and / or an oxygen atom Represents a divalent group having a structure replaced with a group.

[Method for producing acid-modified conjugated diene-based polymer composition]
The method for producing the acid-modified conjugated diene-based polymer composition of the present embodiment (hereinafter, may be abbreviated as “polymer composition”) includes a modified conjugated diene-based polymer having a silicon atom in its structure (hereinafter, referred to as “polymer composition”). , Abbreviated as “modified conjugated diene polymer”) and an organic acid (1) a step of heat-treating at a temperature of 55 ° C. or higher for 45 minutes or more (hereinafter referred to as a step (1)). ) Or (2) a step of kneading at a temperature of 100 ° C. or higher (hereinafter, referred to as step (2)).

  In the case of the step (1), the mixture of the modified conjugated diene polymer and the organic acid is heat-treated at a temperature of 55 ° C. or more for 45 minutes or more to prepare the polymer composition according to the present embodiment. it can. In the case of the step (2), the polymer composition according to the present embodiment can be prepared by kneading a mixture of the modified conjugated diene-based polymer and the organic acid at a temperature of 100 ° C. or higher.

  As a method of mixing the modified conjugated diene-based polymer and the organic acid, for example, a method of mixing the organic acid with the solution of the modified conjugated diene-based polymer can be used. The liquid organic acid may be used after being diluted, and the solid organic acid may be used after being dissolved or melted. The mixing of the modified conjugated diene polymer and the organic acid may be performed in the presence of a solvent. The mixing time of the modified conjugated diene polymer and the organic acid may be from 1 minute to 1 hour. In addition, the temperature at which the modified conjugated diene-based polymer and the organic acid are mixed may be lower than 55 ° C, may be 10 ° C to 50 ° C, or may be 20 ° C to 40 ° C.

  The heat treatment in the step (1) may be performed by raising the temperature to 55 ° C. or higher while mixing the modified conjugated diene polymer and the organic acid, or mixing the modified conjugated diene polymer and the organic acid. It may be carried out afterward at a temperature of 55 ° C. or higher. When the heat treatment in the step (1) is performed while mixing, the heat treatment can be performed by a known stirrer such as a tank with a stirring blade, an in-line mixer, or the like.

  The heat treatment in the step (1) can be performed, for example, while removing the solvent from a mixture of the modified conjugated diene-based polymer, the organic acid, and the solvent. As a method for removing the solvent, for example, a method in which the mixed solution is poured into hot water while stirring and the solvent is removed by steam stripping (for example, see Japanese Patent No. 5815736), and the mixed solution is heated under reduced pressure. To remove the solvent.

  The heat treatment in the step (1) can be performed using, for example, a hot-air drier, a reduced-pressure drier, a thermostat, or the like. The heat treatment temperature is preferably 55C or higher, may be 55 to 220C, may be 60 to 150C, and is more preferably 65 to 120C. The heat treatment time can be adjusted according to the temperature. The heat treatment time is preferably 45 minutes or more and 10 hours or less, more preferably 1 hour or more and 8 hours or less, and still more preferably 1.5 hours or more and 7 hours or less.

  The kneading in the step (2) can be performed using a known kneading machine such as a roll, a Banbury mixer, a kneader, and a twin-screw extruder. The twin-screw extruder is not particularly limited, and a known extruder having a supply port for each component and a vent port for degassing volatile components such as a solvent may be used. The polymer composition can be prepared while removing the solvent from the vent. The twin-screw extruder may be a vent-type single-stage extruder or a vent-type multi-stage extruder. As the twin-screw extruder, a vented extruder as described in JP-A-2011-225805 may be used.

  The kneading temperature in the step (2) is 100 ° C. or higher, preferably 120 to 220 ° C., more preferably 121 to 210 ° C., and further preferably 125 to 200 ° C. The kneading time can be adjusted according to the temperature. The kneading time is preferably 15 seconds or more, more preferably 20 seconds or more and less than 45 minutes, and still more preferably 30 seconds or more and 30 minutes or less. When the kneading is performed at a high temperature for a long time, a mixture of the modified conjugated diene polymer and the organic acid may be deteriorated by a side reaction. Therefore, it is preferable that the kneading is performed in the range of the above conditions.

  The modified conjugated diene-based polymer according to the present embodiment has a group derived from a compound having a silicon atom. The modified conjugated diene-based polymer, after a period of several days to several tens of days, gradually reacts with a part of the group derived from the compound having a silicon atom, and gradually forms a crosslinked structure, It is known that the viscosity increases gradually. In the present invention, by treating the modified conjugated diene-based polymer and the organic acid under specific conditions, a reaction similar to the above-described reaction is caused in the modified conjugated diene-based polymer, and the modified conjugated diene-based polymer is treated. The acid modification suppresses a change in viscosity with time and a cold flow when the polymer composition is stored.

(Organic acid)
The organic acid according to the present embodiment is not particularly limited as long as it is a compound having an acidic group and a hydrocarbon group. Examples of the group exhibiting acidity include a carboxy group, a sulfo group, a hydroxyl group, and a group derived from a phosphate ester. The organic acid is a compound having no group derived from a phosphoric ester, and is preferably a compound having a carboxy group. As the organic acid, an organic carboxylic acid such as an aliphatic carboxylic acid and an aliphatic hydroxycarboxylic acid compound can be suitably used.

  As the aliphatic carboxylic acid, a compound having a hydrocarbon group having 2 to 30 carbon atoms and a carboxy group can be used. Examples of the aliphatic carboxylic acids include saturated fatty acids such as acetic acid, octanoic acid, decanoic acid, undecylic acid, lauric acid, tridecinic acid, myristic acid, pentadecylic acid, palmitic acid, heptadecanoic acid, stearic acid, nonadecylic acid, and arachidic acid. Aromatic carboxylic acids include unsaturated aliphatic carboxylic acids such as palmitoleic acid, oleic acid, ricinolenic acid, linoleic acid, linolenic acid, myristoleic acid, arachidonic acid, icosapentaenoic acid and docosahexaenoic acid. From the standpoint of availability, stearic acid is preferred.

  As the aliphatic hydroxycarboxylic acid compound, an aliphatic compound having a hydroxyl group and a carboxy group can be used. The aliphatic hydroxycarboxylic acid compound preferably has a linear hydrocarbon group, and the hydrocarbon group may have an unsaturated bond. When it has an unsaturated bond, a trans form is preferred. The carbon number of the aliphatic hydroxycarboxylic acid compound is preferably 2 to 40, more preferably 8 to 30.

  Examples of the aliphatic hydroxycarboxylic acid compound include hydroxycaprylic acid, hydroxylauric acid, hydroxypalmitic acid, hydroxystearic acid, dihydroxystearic acid, and hydroxyelaidic acid. Since the cold flow can be further suppressed, the aliphatic hydroxycarboxylic acid compound is preferably 12-hydroxystearic acid or 2-hydroxycaprylic acid, and more preferably 12-hydroxystearic acid.

  By preparing a polymer composition using a modified conjugated diene polymer and an organic acid, it is possible to suppress a change in viscosity with time and a cold flow. The content of the organic acid is preferably more than 0.1 part by mass, more preferably 0.2 to 5 parts by mass, based on 100 parts by mass of the modified conjugated diene-based polymer, in order to further suppress the cold flow. And more preferably 0.25 to 4.5 parts by mass, particularly preferably 0.3 to 4 parts by mass.

(Conjugated diene polymer)
The modified conjugated diene-based polymer according to the present embodiment has units derived from a compound having a silicon atom. The modified conjugated diene-based polymer can be obtained by modifying the conjugated diene-based polymer with a compound having a silicon atom (hereinafter, sometimes referred to as a “modifier”). The conjugated diene-based polymer can be produced by polymerizing a monomer containing a conjugated diene compound using a polymerization initiator. Hereinafter, each component that can be used for producing the modified conjugated diene-based polymer according to the present embodiment will be described.

  Examples of the conjugated diene compound include 1,3-butadiene, isoprene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, 2-phenyl-1, Examples thereof include 3-butadiene, 4,5-diethyl-1,3-octadiene, 3-butyl-1,3-octadiene and 1,3-hexadiene, and preferably 1,3-butadiene or isoprene. These conjugated diene compounds may be used alone or in combination of two or more.

  The monomer according to this embodiment can include an aromatic vinyl compound together with the conjugated diene compound. Examples of the aromatic vinyl compound include styrene, α-methylstyrene, vinyltoluene, vinylnaphthalene, divinylbenzene, trivinylbenzene, and divinylnaphthalene, and styrene is preferable.

  The content of the aromatic vinyl compound in the monomer is preferably 5% by mass or more, more preferably 10% by mass or more, with the total amount of the monomer being 100% by mass. Further, the content of the aromatic vinyl compound is preferably 50% by mass or less, more preferably 45% by mass or less, and further preferably 40% by mass or less, in order to enhance fuel economy.

  The modified conjugated diene-based polymer according to the present embodiment has a conjugated diene monomer unit, a modifier monomer unit, and another monomer unit other than the aromatic vinyl monomer unit. Good. Other monomers include chain olefin compounds such as ethylene, propylene, and 1-butene; cyclic olefin compounds such as cyclopentene and 2-norbornene; 1,5-hexadiene, 1,6-heptadiene, and 1,7-octadiene. , Dicyclopentadiene, and non-conjugated diene compounds such as 5-ethylidene-2-norbornene. The content ratio of the other monomer units in the conjugated diene polymer chain according to the present embodiment is preferably 10% by mass or less, more preferably 5% by mass or less.

  The modified conjugated diene-based polymer according to the present embodiment includes a polymer block (A) having an isoprene monomer unit as a main component and a polymer block (B) having a 1,3-butadiene monomer unit as a main component. ) May be provided.

  Mw of the polymer block (A) is preferably from 1,000 to 30,000. The polymer block (A) is not particularly limited as long as it is mainly composed of isoprene monomer units, and may be composed of only isoprene monomer units, or may be composed of isoprene monomer units. It may be composed of a unit and a monomer unit other than isoprene. As a monomer other than isoprene, an aromatic vinyl compound may be used. The polymer block (A) may contain an isoprene monomer unit and an aromatic vinyl monomer unit.

  The content ratio of the isoprene monomer unit in the polymer block (A) is preferably 50% by mass or more, more preferably 70% by mass or more, and further preferably 90% by mass or more. The upper limit of the content ratio of the isoprene monomer unit is not particularly limited, but is preferably 99% by mass or less. By setting the content ratio of the isoprene monomer unit in the polymer block (A) to the above range, when a reinforcing material such as silica is mixed with the conjugated diene-based polymer, the conjugated diene-based polymer and the silica or the like can be mixed. The affinity with the reinforcing material can be further increased, and the resulting rubber crosslinked product can be made to have excellent low heat build-up and wet grip properties.

  Examples of the polymerization initiator include an alkali metal, a complex of an alkali metal and a polar compound, an oligomer having an alkali metal, an organic alkali metal compound, a Ziegler-Natta catalyst, and a metallocene catalyst. The polymerization initiator is preferably an organic alkali metal compound. The polymerization initiators may be used alone or in combination of two or more.

  Examples of the alkali metal include lithium, sodium, potassium, rubidium and cesium. Examples of the complex of an alkali metal and a polar compound include a potassium-tetrahydrofuran complex and a potassium-diethoxyethane complex. Examples of the oligomer having an alkali metal include a sodium salt of α-methylstyrene tetramer.

  Examples of the organic alkali metal compound include an organic alkali metal compound having a group containing a nitrogen atom and an organic alkali metal compound having a hydrocarbyl group.

  Examples of the organic alkali metal compound having a hydrocarbyl group include, for example, ethyl lithium, n-propyl lithium, isopropyl lithium, n-butyl lithium, sec-butyl lithium, tert-butyl lithium, tert-octyl lithium, n-decyl lithium, phenyl Lithium, 2-naphthyllithium, 2-butylphenyllithium, 4-phenylbutyllithium, cyclohexyllithium, cyclopentyllithium, 1,4-dilithiobutane, 1,4-dilithio-2-butene, 1,3,5-trilithiobenzene 1,3,5-tris (lithiomethyl) benzene, 2,3,5-tris (lithiomethyl) naphthalene, 1,4,5-tris (lithiomethyl) naphthalene, 1,3,3-trilithiooctyne, sodium naphthalene Do, na It includes potassium biphenylide and potassium naphthalenide, preferably n- butyllithium.

  Examples of the organic alkali metal compound having a group containing a nitrogen atom include, for example, methylaminopropyllithium, diethylaminopropyllithium, tert-butyldimethylsilyloxypropyllithium, N-morpholinopropyllithium, lithium hexamethyleneimide, lithium pyrrolidide, A group containing a nitrogen atom such as a compound obtained by reacting isoprene with lithium piperidide, lithium heptamethyleneimide, lithium dodecamethyleneimide, 3- (dimethylamino) propyllithium or 3- (diethylamino) propyllithium Organic alkali metal compounds.

The organic alkali metal compound having a group containing a nitrogen atom is preferably an organic alkali metal compound having a group represented by the following formula (2).

In the formula (2), R ²¹ and R ²² each independently represent a hydrocarbyl group or a trihydrocarbylsilyl group which may have a substituent, or a part of R ²¹ and one of R ²² and a part formed by combining a nitrogen atom and / or hydrocarbylene group optionally having an oxygen _{^{atom, -Si (R 32) 2 -}} (CH 2) x -Si (R 32) 2 - Table carbon atoms 5 to 20 of groups ^{(. R 32} represents a hydrocarbyl group, x is 1 to 10 integer), _{^{or, -Si (R 33) 2 -}} (CH 2) y - in It may form a group having 4 to 20 carbon atoms (R ³³ represents a hydrocarbyl group, and y is an integer of 2 to 11).

Examples of the hydrocarbyl group for R ²¹ and R ²² include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, and an aralkyl group. Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an n-hexyl group, and an n-octyl group. , N-dodecyl group, cyclopentyl group and cyclohexyl group. Examples of the alkenyl group include a vinyl group, an aryl group, a 1-propenyl group and an isopropenyl group. Examples of the alkynyl group include an ethynyl group and a 2-propynyl group. Examples of the aryl group include a phenyl group, a methylphenyl group, an ethylphenyl group, a benzyl group, a tolyl group, and a xylyl group. Examples of the aralkyl group include a benzyl group. The hydrocarbyl group is preferably an alkyl group, more preferably an alkyl group having 1 to 4 carbon atoms.

Examples of the hydrocarbyl group having a substituent in R ²¹ and R ²² include a hydrocarbyl group in which one or more hydrogen atoms are substituted with a substituted amino group, a hydrocarbyl group in which one or more hydrogen atoms are substituted with a hydrocarbyloxy group, Examples thereof include a hydrocarbyl group in which the above hydrogen atoms are substituted with a trialkylsilyl group, and a hydrocarbyl group in which one or more hydrogen atoms are substituted with a trialkoxysilyl group.

  Here, examples of the substituted amino group include N, N-dimethylamino group, N, N-dialkylamino group such as N, N-diethylamino group, 1-pyrrolyl group, 1-piperidyl group, 1-imidazolyl group and the like. A cyclic amino group.

  Examples of the hydrocarbyl group in which one or more hydrogen atoms have been substituted with a substituted amino group include, for example, an N, N-dimethylaminomethyl group, a 2- (N, N-dimethylamino) ethyl group, and a 2- (N, N-diethylamino) group. ) Ethyl, 3- (N, N-dimethylamino) propyl, 3- (N, N-diethylamino) propyl and other (N, N-dialkylamino) alkyl groups; 4- (N, N-dimethylamino) ) Phenyl, 3- (N, N-dimethylamino) phenyl, 4- (N, N-diethylamino) phenyl, 3- (N, N-diethylamino) phenyl, and other (N, N-dialkylamino) Aryl group; (N, N-dialkylamino) alkyl such as 4- (N, N-dimethylamino) methylphenyl group and 4- [2- (N, N-dimethylamino) ethyl] phenyl group Reel group; an alkyl group substituted with a cyclic amino group such as a 3- (1-pyrrolidinyl) propyl group, a 3- (1-piperidinyl) propyl group, or a 3- (1-imidazolyl) propyl group; 4- (1-pyrrolidinyl) An aryl group substituted with a cyclic amino group such as a phenyl group, a 4- (1-piperidinyl) phenyl group or a 4- (1-imidazolyl) phenyl group; a 4- [2- (1-pyrrolidinyl) ethyl] phenyl group; Examples thereof include an alkylaryl group substituted with a cyclic amino group such as a 4- [2- (1-piperidinyl) ethyl] phenyl group and a 4- [2- (1-imidazolyl) ethyl] phenyl group.

Examples of the hydrocarbyl group in which one or more hydrogen atoms are substituted with a hydrocarbyloxy group include an alkoxyalkyl group such as a methoxymethyl group, an ethoxymethyl group, a methoxyethyl group, and an ethoxyethyl group.
Examples of the hydrocarbyl group in which one or more hydrogen atoms have been substituted with a trialkylsilyl group include trialkylsilylalkyl groups such as a trimethylsilylmethyl group, a 2-trimethylsilylethyl group, and a 3-trimethylsilylpropyl group.
Examples of the hydrocarbyl group in which one or more hydrogen atoms are substituted with a trialkoxysilyl group include trialkoxysilylalkyl groups such as a trimethoxysilylmethyl group, a 2-trimethoxysilylethyl group, and a 3-trimethoxysilylpropyl group. Can be mentioned.

  As the hydrocarbyl group which may have a substituent, a hydrocarbyl group which may have a substituent having 1 to 20 carbon atoms is preferable, and a hydrocarbyl group having 1 to 20 carbon atoms is more preferable. An alkyl group having 1 to 10 carbon atoms is more preferable, and a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group or a tert-butyl group is more preferable. Groups or ethyl groups are particularly preferred.

Examples of the trihydrocarbylsilyl group for R ²¹ and R ²² include, for example, trimethylsilyl group, triethylsilyl group, tripropylsilyl group, triisopropylsilyl group, tributylsilyl group, tripentylsilyl group, trihexylsilyl group, tert-butyl- Examples thereof include a trialkylsilyl group such as a dimethylsilyl group, and a trimethylsilyl group or a triethylsilyl group is preferable.

The hydrocarbylene group which may have a nitrogen atom and / or an oxygen atom formed by combining a part of R ^{21 and} a part of R ²² is a hydrocarbylene group or a nitrogen atom and / or It is a hydrocarbylene group having an oxygen atom.

  Examples of the hydrocarbylene group include an alkylene group, an alkenediyl group, an arylene group, and a group in which an arylene group is bonded to an alkylene group (hereinafter, may be referred to as an arylene-alkylene group). Examples of the alkylene group include a methylene group, an ethylene group, a propylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, a heptamethylene group, an octamethylene group, and 2,2,4-trimethylhexane-1,6- Diyl groups can be mentioned. Examples of the alkenediyl group include a pentane-2-ene-1,5-diyl group. Examples of the arylene group include a phenylene group, a naphthylene group, and a biphenylene group. Examples of the arylene-alkylene group include a phenylene-alkylene group, a naphthylene-alkylene group, and a biphenylene-alkylene group. The hydrocarbylene group is preferably an alkylene group, more preferably an alkylene group having 4 to 7 carbon atoms.

The hydrocarbylene group having a nitrogen atom and / or oxygen atoms, for example, -CH = N-CH = CH- group represented _{by, -CH = N-CH 2 -CH} 2 - , a group represented by _{-CH 2 -CH 2 -O-CH 2} -CH 2 - group represented by like can be mentioned, _{preferably, -CH = N-CH 2 -CH} 2 -, or _-CH 2 -CH ₂ - _{O-CH 2} -CH 2 - is a group represented by.
As the hydrocarbylene group which may have a nitrogen atom and / or an oxygen atom, a hydrocarbylene group which may have a nitrogen atom and / or an oxygen atom having 3 to 20 carbon atoms is preferable, A hydrocarbylene group having 3 to 20 carbon atoms is preferred, an alkylene group having 4 to 7 carbon atoms is more preferred, and a tetramethylene group, pentamethylene group or hexamethylene group is still more preferred.

A portion is formed by bonding ^-Si part and ^{R 22} of _{^{R 21 (R 35) 2 -}} (CH 2) x -Si (R 35) 2 - 20 The following 5 or more carbon atoms represented by group ^{(R 35} represents a hydrocarbyl group, x is an integer of 1 to 10.) _{the, -Si (CH 3) 2 -CH} 2 -CH 2 -Si (CH 3) 2 - is represented by And the like.
A group having 4 to 20 carbon atoms represented by —Si (R ³⁶ ) ₂ — (CH ₂ ) _y — formed by combining a part of R ^{21 and} a part of R ²² (R ³⁶ is a hydrocarbyl group the stands, y as stands) an integer of 2 to _{11, -Si (CH 3) 2 -CH} 2 -CH 2 -CH 2 -. and the groups represented by like.

It is preferable that R ²¹ and R ²² each independently represent a hydrocarbyl group or a hydrocarbylene group formed by combining a part of R ^{21 and} a part of R ^22. Represents an alkyl group having 1 to 4 carbon atoms or an alkylene group having 4 to 7 carbon atoms formed by combining a part of R ^{21 and} a part of R ^22. More preferably, each independently represents an alkyl group having 1 to 4 carbon atoms, and more preferably each independently represents a methyl group or an ethyl group.

  Specific examples of the organic alkali metal compound having a group represented by the formula (2) include dimethylaminopropyllithium, diethylaminopropyllithium, tert-butyldimethylsilyloxypropyllithium, N-morpholinopropyllithium, lithium hexamethyleneimide , Lithium pyrrolidide, lithium piperidide, lithium heptamethyleneimide, lithium dodecamethyleneimide and the like.

式（３）中、Ｒ^２１及びＲ^２２は、それぞれ、式（２）におけるＲ^２１及びＲ^２２と同義であり、Ｒ^３１は炭素原子数６以上１００以下のヒドロカルビレン基を表し、Ｍはアルカリ金属原子を表す。 As a method for producing an organic alkali metal compound having a group represented by the formula (2), a method using a compound represented by the formula (3), a method using an organic alkali metal compound and a group represented by the formula (2) A method of reacting with a secondary amine compound can be used.

In Formula (3), R ²¹ and R ²² have the same meanings as R ²¹ and R ²² in Formula (2), respectively, and R ³¹ represents a hydrocarbylene group having 6 to 100 carbon atoms, and M represents Represents an alkali metal atom.

The hydrocarbylene group having 6 to 100 carbon atoms of R ³¹ is preferably a hydrocarbylene group having 7 to 90 carbon atoms, and more preferably a hydrocarbylene group having 8 to 80 carbon atoms. is there.

式（３−１）中、Ｒ^３４は共役ジエン化合物由来の構造単位及び／又は芳香族ビニル化合物由来の構造単位を表し、ｉ及びｆは１以上１０以下の整数である。なお、式（３−１）中の−（ＣＨ_２）_ｉが式（３）の窒素原子に結合し、Ｒ^３４が式（３）のＭに結合する。 The hydrocarbylene group having 8 to 80 carbon atoms of R ³¹ is preferably a group represented by the formula (3-1).

Wherein (3-1), R ³⁴ represents a structural unit derived structural unit and / or an aromatic vinyl compound derived from a conjugated diene compound, the i and f is 1 to 10 integer. Incidentally, the formula (3-1) in the - _{(CH 2) i} is bonded to the nitrogen atom of formula ^{(3), R 34} is bonded to M of the formula (3).

The structural unit derived from the conjugated diene compound and / or the structural unit derived from the aromatic vinyl compound in R ³⁴ is preferably a structural unit derived from isoprene, a structural unit derived from styrene, or a structural unit derived from butadiene.
f is preferably an integer of 1 or more and 5 or less.
i is preferably an integer of 2 or more and 4 or less, and more preferably 3.

As the group represented by the above formula (3-1), preferably, R ³⁴ is a structural unit derived from isoprene, i is 1; R ³⁴ is a structural unit derived from isoprene; A group or a group in which R ³⁴ represents a structural unit derived from isoprene, and i is 3.
Examples of the alkali metal atom of M include lithium, sodium, potassium and cesium, and preferably lithium.

In the compound represented by the formula (3), R ³¹ represents a group represented by the formula (3-1), R ²¹ and R ²² each independently represent a hydrocarbyl group, and M represents lithium. Examples of the compound represented include a compound obtained by reacting (dialkylamino) alkyllithium compound with isoprene. Such compounds include, for example, 3- (dimethylamino) propyl lithium, 3- (diethylamino) propyl lithium, 3- (dibutylamino) propyl lithium, 4- (dimethylamino) butyl lithium, 4- (diethylamino) butyl lithium , 4- (dipropylamino) butyllithium and 3- (dibutylamino) butyllithium.

In the compound represented by the formula (3), R ³¹ represents a group represented by the formula (3-1), and R ²¹ and R ²² form a bond between a part of R ^{21 and} a part of R ^22. As a compound in which M represents lithium, a compound obtained by reacting isoprene with an alkyllithium compound having a cyclic amino group can be exemplified. Examples of the alkyl lithium compound having a cyclic amino group include 3- (1-pyrrolidinyl) propyl lithium, 3- (1-piperidinyl) propyl lithium, 3- (1-hexamethyleneimino) propyl lithium, and 3- [1- (1,2,3,6-tetrahydropyridinyl)] propyl lithium.

In the compound represented by the formula (3), R ³¹ represents a group represented by the formula (3-1), and R ²¹ and R ²² form a bond between a part of R ^{21 and} a part of R ^22. Examples of the compound in which M represents lithium, which represents a hydrocarbylene group having a nitrogen atom and / or an oxygen atom, include compounds obtained by reacting isoprene with an alkyllithium compound having a cyclic amino group. it can. Examples of the alkyl lithium compound having a cyclic amino group include 3- (1-morpholino) propyl lithium, 3- (1-imidazolyl) propyl lithium and 3- (4,5-dihydro-1-imidazolyl) propyl lithium. be able to.

In the compound represented by the formula (3), R ³¹ represents a group represented by the formula (3-1), and R ²¹ and R ²² form a bond between a part of R ^{21 and} a part of R ^22. and comprising _{^{-Si (R 35) 2 - (}} CH 2) x -Si (R 35) 2 - 20 the following group having 5 or more carbon atoms represented by ^{(R 35} represents a hydrocarbyl group, x is 1 or more And the compound in which M represents lithium is 3- (2,2,5,5-tetramethyl-1-aza-2,5-disila-1-cyclopentyl) propyl lithium And isoprene, butadiene, or styrene.

In the compound represented by the formula (3), R ³¹ represents a group represented by the formula (3-1), and R ²¹ and R ²² form a bond between a part of R ^{21 and} a part of R ^22. and ^-Si comprising _{(R 36) 2 - (CH} 2) y - carbon atoms represented by 4 to 20 of the group ^{(R 36} represents a hydrocarbyl group, y is 2 to 11 integers. ) Wherein M represents lithium, which is obtained by reacting 3- (2,2-dimethyl-1-aza-2-sila-1-cyclopentyl) propyl lithium with isoprene, butadiene or styrene. And the like.

As the compound represented by the formula (3), preferably, R ³¹ represents a group represented by the formula (3-1), R ²¹ and R ²² each independently represent a hydrocarbyl group, and M represents R ²¹ and R ²² each independently represent an alkyl group having 1 to 4 carbon atoms, M represents lithium, and R ³¹ represents a compound represented by the formula (3-1) Wherein R ³⁴ in the formula (3-1) represents a structural unit derived from isoprene, f is 1 or more and 5 or less, and i is 2 or more and 4 or less, more preferably a compound represented by the following formula: Is a compound obtained by reacting 3- (dimethylamino) propyllithium or 3- (diethylamino) propyllithium with isoprene.

  Two or more compounds represented by the formula (3) may be used in combination.

  As the polymerization initiator, a conjugated diene polymer having an active terminal may be used. The conjugated diene-based polymer having an active terminal can be obtained by reacting a polymerization initiator with a monomer containing a conjugated diene compound. As the polymerization initiator, the same compounds as those described above can be used. The monomer used for the conjugated diene-based polymer having an active terminal is not particularly limited. Examples of the monomer include a conjugated diene compound, an aromatic vinyl compound, and a compound copolymerizable with a conjugated diene compound. Can be used. The conjugated diene polymer having an active terminal preferably contains only isoprene as a monomer unit, or contains isoprene and an aromatic vinyl compound.

The modifier can include a compound having a structure represented by the formula (5).

In the formula (5), R ¹ represents an alkyl group, an alkenyl group, a cycloalkenyl group or an aryl group, M ¹ represents a silicon atom, a tin atom, a germanium atom or a phosphorus atom, and L ¹ represents a halogen atom or a hydrocarbyloxy group. And when there are a plurality of R ¹ and L ¹ , they may be the same or different, and when M ¹ is a silicon atom, a tin atom or a germanium atom, n represents 0, and m and l are each independently represents an integer of 0 to 4 that satisfies m + 1 = 4, and when M ¹ is a phosphorus atom, n represents 0 or 1, and m and l each independently represent an integer of 0 to 3 that satisfies m + 1 = 3.

As the alkyl group for R ¹ , an alkyl group having 1 to 12 carbon atoms is preferable, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group and a tert-butyl group. And n-pentyl, n-hexyl, n-octyl, n-dodecyl, cyclopentyl and cyclohexyl. As the alkenyl group, an alkenyl group having 2 to 12 carbon atoms is preferable, and examples thereof include a vinyl group, an allyl group, a 1-propenyl group and an isopropenyl group. As the aryl group, an aryl group having 6 to 12 carbon atoms is preferable, and examples thereof include a phenyl group, a methylphenyl group, an ethylphenyl group, a benzyl group, a tolyl group and a xylyl group.

In L ^1, examples of the halogen atom include chlorine atom, a bromine atom and an iodine atom. Examples of the hydrocarbyloxy group include an alkoxy group and an aryloxy group. As the alkoxy group, an alkoxy group having 1 to 12 carbon atoms is preferable, for example, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, tert-butoxy group, pentyl Oxy, hexyloxy, heptyloxy and octyloxy groups are exemplified. As the aryloxy group, an aryloxy group having 6 to 12 carbon atoms is preferable, and examples thereof include a phenoxy group and a benzyloxy group.

Examples of the compound having the structure represented by the formula (5), for example, a silane compound M ¹ is a silicon atom, a tin compound M ¹ is a tin atom, M ¹ is the germanium compound and M ¹ is a germanium atom And a phosphorus compound which is a phosphorus atom.

  As the silane compound, for example, silicon tetrachloride, silicon tetrabromide, silicon tetraiodide, methyltrichlorosilane, dimethyldichlorosilane, ethyltrichlorosilane, butyltrichlorosilane, hexyltrichlorosilane, tetramethoxysilane, methyltrimethoxysilane, Dimethoxydimethylsilane, chlorotrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, dimethoxydiethylsilane, diethoxydimethylsilane, tetraethoxysilane, ethyltriethoxysilane, diethoxydiethylsilane, dichlorodimethoxysilane and trichloromethoxysilane No.

  Examples of the tin compound include tin tetrachloride, monomethyltrichlorotin, monoethyltrichlorotin, monobutyltrichlorotin, monophenyltrichlorotin, tetramethoxytin, and tetraethoxytin.

  As the germanium compound, for example, germanium tetrachloride, germanium tetrabromide, germanium tetraiodide, methyltrichlorogermanium, ethyltrichlorogermanium, phenyltrichlorogermanium, dimethyldichlorogermanium, diethyldichlorogermanium, dibutyldichlorogermanium, diphenyldichlorogermanium, tetra Examples include methoxygermanium, tetraethoxygermanium, tetraisopropoxygermanium and tetrabutoxygermanium.

  Examples of the phosphorus compound include, for example, trichlorophosphine, a halogenated phosphorus compound such as tribromophosphine, trisnonylphenyl phosphite, trimethyl phosphite, a phosphite compound such as triethyl phosphite, trimethyl phosphate, triethyl phosphate and the like. Phosphate ester compounds are exemplified.

  The amount of the polymerization initiator to be used is preferably 0.01 mmol to 15 mmol per 100 g of the total amount of the monomers.

  The polymerization of the monomer is preferably performed in a hydrocarbon solvent. As the hydrocarbon solvent, an aliphatic hydrocarbon, an aromatic hydrocarbon, an alicyclic hydrocarbon, or the like can be used. The hydrocarbon solvent may be used alone or in combination of two or more, and a mixture of an aliphatic hydrocarbon and an alicyclic hydrocarbon such as industrial hexane may be used.

  Examples of the aliphatic hydrocarbon include, for example, propane, n-butane, iso-butane, n-pentane, iso-pentane, 2-methylpentane, 3-methylpentane, n-hexane, propene, 1-butene, iso-butene , Trans-2-butene, cis-2-butene, 1-pentene, 2-pentene, 1-hexene and 2-hexene. Examples of the aromatic hydrocarbon include benzene, toluene, xylene and ethylbenzene. Alicyclic hydrocarbons include, for example, cyclopentane, cyclohexane and methylcyclopentane.

  When polymerizing a monomer in a solvent, the concentration of the monomer in the solvent is usually 1 to 50% by mass, preferably 5 to 30% by mass. The polymerization temperature is usually from 25 to 100 ° C, preferably from 35 to 90 ° C, and more preferably from 50 to 80 ° C. The polymerization time is usually from 10 minutes to 5 hours.

  The modified conjugated diene-based polymer according to this embodiment has a unit derived from a compound having a silicon atom, which is a modifier, at either the terminal of the polymer or in the molecular chain. The unit may be present at the terminal, in the molecular chain, or at the terminal and in the molecular chain of the conjugated diene polymer. The compound having a silicon atom may be a compound having an alkoxysilyl group, and the modified conjugated diene-based polymer may have a terminal based on the compound having an alkoxysilyl group at the terminal.

As the modifier, a compound having a structure represented by the formula (6) can be used. By reacting a polymer obtained by polymerizing a monomer containing a conjugated diene compound with a compound having a structure represented by the formula (6), a polymer having a structure represented by the formula (6) is obtained. A modified conjugated diene polymer having a unit at the terminal can be obtained.

Represents in the formula (6), the X ^1, X ² and X ³ are each independently, a hydrocarbyl group, hydrocarbyloxy group, a halogen atom, or a functional group capable of reacting with the active terminal of the conjugated diene polymer, R ⁶¹ And R ⁶² each independently represent a hydrogen atom or a hydrocarbyl group, and when there are a plurality of R ⁶¹ and R ⁶² , they may be the same or different. A ¹ is an organic group having at least one atom selected from the group consisting of an oxygen atom, a nitrogen atom, a phosphorus atom, a sulfur atom and a silicon atom (any one of an oxygen atom, a nitrogen atom, a phosphorus atom, a sulfur atom and a silicon atom) A ¹ may have a ring structure, and a part of the structure of X ¹ , X ² or X ³ may be bonded to a part of A ¹ Good. That is, A ¹ may be bonded to the silicon atom in the formula (6) via X ¹ , X ² or X ³ . a represents an integer of 0 to 10.

Examples of the hydrocarbyl group in X ¹ , X ² and X ³ include an alkyl group, an aryl group, an alkenyl group and an aralkyl group. The alkyl group is preferably an alkyl group having 1 to 12 carbon atoms, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, n-pentyl, n-hexyl, n-octyl, n-dodecyl, cyclopentyl and cyclohexyl. The aryl group is preferably an aryl group having 6 to 12 carbon atoms, and includes a phenyl group, a methylphenyl group, an ethylphenyl group, a benzyl group, a tolyl group and a xylyl group. The alkenyl group is preferably an alkenyl group having 2 to 12 carbon atoms, for example, a vinyl group, an allyl group, a 1-propenyl group and an isopropenyl group. Examples of the aralkyl group include a benzyl group.
Examples of the hydrocarbyloxy group include an alkoxy group and an aryloxy group. The alkoxy group is preferably an alkoxy group having 1 to 12 carbon atoms, such as a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group and a tert-butoxy group. Is mentioned. The aryloxy group is preferably an aryloxy group having 6 to 12 carbon atoms, for example, a phenoxy group and a benzyloxy group. The hydrocarbyloxy group is preferably an alkoxy group, more preferably a methoxy group or an ethoxy group.
Examples of the halogen atom include a chlorine atom, a bromine atom and an iodine atom.
Examples of the functional group capable of reacting with the active terminal of the conjugated diene polymer include a hydrocarbon group having an epoxy group and a hydrocarbon group having a carbonyl group.

The hydrocarbyl group in R ⁶¹ and R ⁶² is preferably a hydrocarbyl group having 1 to 4 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, and still more preferably a methyl group or an ethyl group. is there. If R ⁶¹ is plural, R ⁶¹ may be different be the same as each other, if R ⁶² is plural, R ⁶² may be different be the same as each other.
a is preferably 3 or more from the viewpoint of enhancing fuel economy, and is preferably 4 or less from the viewpoint of improving economical efficiency during manufacturing.

The A ¹ is an organic group having at least nitrogen atom, for example, a group represented by the formula (6-1).

In the formula (6-1), R ⁶³ and R ⁶⁴ each independently represent a hydrocarbyl group or a trihydrocarbylsilyl group which may have a substituent, or a part of R ⁶³ and one of R ⁶⁴ And a hydrocarbylene group optionally having at least one atom selected from the group consisting of a silicon atom, a nitrogen atom and an oxygen atom.

Here, when a part of R ^{63 and} a part of R ⁶⁴ are not bonded, the group represented by the formula (6-1) is an acyclic amino group, and R ⁶³ and R ⁶⁴ are bonded to each other. If it is, it is a cyclic amino group.

The hydrocarbyl group which may have a substituent in R ⁶³ and R ⁶⁴ is a hydrocarbyl group or a substituted hydrocarbyl group.
Examples of the hydrocarbyl group include alkyl groups having 1 to 12 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group and n-butyl group; and carbon atoms such as vinyl group, allyl group and isopropenyl group. An alkenyl group having 2 to 12 carbon atoms; an aryl group having 6 to 12 carbon atoms such as a phenyl group and a benzyl group; preferably an alkyl group or an aryl group, more preferably a methyl group, an ethyl group or a benzyl group; Group.
Examples of the substituted hydrocarbyl group include an oxacycloalkyl group such as an oxiranyl group and a tetrahydrofuranyl group, and a tetrahydrofuranyl group is preferable.

In the present specification, the oxacycloalkyl group represents a group in which CH ₂ on the alicyclic ring of the cycloalkyl group is replaced with an oxygen atom.

Examples of the trihydrocarbylsilyl group for R ⁶³ and R ⁶⁴ include a trimethylsilyl group and a tert-butyl-dimethylsilyl group, and a trimethylsilyl group is preferable.

A hydrocarbylene group optionally having at least one atom selected from the group consisting of a silicon atom, a nitrogen atom and an oxygen atom, in which a part of R ^{63 and} a part of R ⁶⁴ are bonded, is a hydrocarbyl group. It is a carbylene group or a hydrocarbylene group having at least one atom selected from the group consisting of a silicon atom, a nitrogen atom and an oxygen atom (heteroatom-containing hydrocarbylene group).
Examples of the hydrocarbylene group include an alkylene group having 2 to 12 carbon atoms such as a tetramethylene group, a pentamethylene group, a hexamethylene group, and a 2,2,4-trimethylhexane-1,6-diyl group. Among them, an alkylene group having 4 to 7 carbon atoms is preferable, and a pentamethylene group or a hexamethylene group is particularly preferable.
Examples of the hetero atom-containing hydrocarbylene group include a silicon atom-containing hydrocarbylene group, a nitrogen atom-containing hydrocarbylene group, and an oxygen atom-containing hydrocarbylene group.
Examples of the silicon-containing hydrocarbylene group include, for example, a group represented by —Si (CH ₃ ) ₂ —CH ₂ —CH ₂ —Si (CH ₃ ) ₂ —. Examples of the nitrogen atom-containing hydrocarbylene group, e.g., -CH = N-CH = CH- group represented by and _{-CH = N-CH 2 -CH 2} - can be mentioned a group represented by. Examples of the oxygen-containing hydrocarbylene group include, for example, a group represented by —CH ₂ —CH ₂ —O—CH ₂ —CH ₂ —.

The A ¹ is an organic group having at least an oxygen atom, for example, a group represented by the formula (6-2).

In the formula (6-2), X ⁴ represents a hydrocarbylene group having 1 to 6 carbon atoms which may have an oxygen atom, and R ⁶⁵ represents a hydrogen atom or a hydrocarbyl group having 1 to 6 carbon atoms. Represents a group.

Examples of the hydrocarbylene group having 1 to 6 carbon atoms which may have an oxygen atom in X ⁴ include, for example, an unsubstituted hydrocarbylene group and a group having an oxygen atom as a substituent. Hydrocarbylene groups may be mentioned.
As X ^4, specifically, there may be mentioned hydrocarbylene group and hydrocarbylene group, more specifically, ethylene group, propylene group, butylene group, 1-oxyethylene group, 1-oxytri Examples include a methylene group and a 1-oxytetramethylene group. X ⁴ is preferably a 1-oxytrimethylene group.

In R ^65, examples of the hydrocarbyl group having 1 to 6 carbon atoms, for example, may be mentioned alkyl group and aryl group include a methyl group, an ethyl group, n- propyl group, an isopropyl radical, n -Butyl group, sec-butyl group, t-butyl group, n-pentyl group, neopentyl group, isopentyl group, n-hexyl group, cyclohexyl group and phenyl group. R ⁶⁵ is preferably a hydrogen atom or a methyl group.

The A ¹ is an organic group having at least a sulfur atom, for example, a group represented by the formula (6-3).

In the formula (6-3), R ⁶⁶ represents a trihydrocarbylsilyl group. Examples of the trihydrocarbylsilyl group include a trimethylsilyl group, a triethylsilyl group, and a tert-butyl-dimethylsilyl group, and a trimethylsilyl group or a triethylsilyl group is preferable.

The A ¹ is an organic group having at least silicon atoms, for example, a group represented by the formula (6-4). That is, the compound represented by the formula (6), for example, a polyorganosiloxane compound having a group represented by the formula (6-4) as A ^1.

In the formula (6-4), R ⁶⁶ , R ⁶⁷ and R ⁶⁸ each independently represent a hydrocarbyl group or a group having a hydrocarbyleneoxy group, and X ⁵ and X ⁶ each independently represent A group containing a repeating unit of a hydrocarbyl group, a hydrocarbyloxy group, a hydrocarbyleneoxy group, a halogen atom, or a functional group capable of reacting with an active terminal of a conjugated diene polymer and / or a modifying agent; Represents an integer of ~ 600, and a plurality of R ⁶⁶ and X ⁵ may be the same or different.

Examples of the hydrocarbyl group in R ⁶⁶ , R ⁶⁷ , R ⁶⁸ , X ⁵ and X ⁶ include, for example, an alkyl group, an aryl group and an aralkyl group. As the alkyl group, an alkyl group having 1 to 12 carbon atoms is preferable. For example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, an n- Examples include a pentyl group, an n-hexyl group, an n-octyl group, an n-dodecyl group, a cyclopentyl group and a cyclohexyl group. As the aryl group, an aryl group having 6 to 12 carbon atoms is preferable, and examples thereof include a phenyl group, a methylphenyl group, an ethylphenyl group, a tolyl group, and a xylyl group. The aralkyl group is preferably an aralkyl group having 7 to 13 carbon atoms, for example, a benzyl group.
Examples of the group having a repeating unit of a hydrocarbyleneoxy group in R ⁶⁶ , R ⁶⁷ , R ⁶⁸ , X ⁵ and X ⁶ include a group having a repeating unit based on alkylene glycol. Examples of the hydrocarbyleneoxy group include a 1-oxyethylene group, a 1-oxytrimethylene group, and a 1-oxytetramethylene group, and a 1-oxyethylene group is preferable.

Examples of the hydrocarbyloxy group in X ⁵ and X ⁶ include an alkoxy group and an aryloxy group. As the alkoxy group, an alkoxy group having 1 to 12 carbon atoms is preferable, for example, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, tert-butoxy group, pentyl Oxy, hexyloxy, heptyloxy and octyloxy groups are exemplified. As the aryloxy group, an aryloxy group having 6 to 12 carbon atoms is preferable, and examples thereof include a phenoxy group and a benzyloxy group.
Examples of the halogen atom include a chlorine atom, a bromine atom and an iodine atom.
Examples of the functional group capable of reacting with the active terminal of the conjugated diene-based polymer and / or the modifying agent include a group having 4 to 12 carbon atoms having an epoxy group and a hydrocarbon group having a carbonyl group.

Examples of the group having 4 to 12 carbon atoms having an epoxy group include a group represented by the following formula (6-4-1).
-Z ¹ -Z ² -E (6-4-1)
In the formula (6-4-1), Z ¹ is an alkylene group or an alkyl arylene group having 1 to 10 carbon atoms, Z ² is a methylene group, a sulfur atom or an oxygen atom, and E is a carbon atom having an epoxy group. It is a hydrocarbon group of several 2 to 10.

As the group represented by the formula (6-4-1), a group in which Z ² is an oxygen atom is preferable, a group in which Z ² is an oxygen atom and E is a glycidyl group is more preferable, and Z ¹ Is an alkylene group having 1 to 3 carbon atoms, Z ² is an oxygen atom, and E is a glycidyl group.

  g is preferably from 3 to 360 from the viewpoint of handling, and is preferably from 4 to 120 from the viewpoint of fuel saving performance.

Among the compounds having a structure represented by the formula (6), compounds in which A ¹ is an acyclic amino group represented by the formula (6-1) include, for example, [3- (dimethylamino) propyl] trimethoxy Silane, [3- (diethylamino) propyl] trimethoxysilane, [3- (dimethylamino) propyl] triethoxysilane, [3- (diethylamino) propyl] triethoxysilane, [3- (ethylmethylamino) propyl] trisilane Methoxysilane, [3- (ethylmethylamino) propyl] triethoxysilane, [3- (dimethylamino) propyl] methyldimethoxysilane, [3- (diethylamino) propyl] methyldimethoxysilane, [3- (dimethylamino) propyl ] Ethyldimethoxysilane, [3- (diethylamino) propyl] ethyldimethoate Xysilane, [3- (dimethylamino) propyl] dimethylmethoxysilane, [3- (dimethylamino) propyl] diethylmethoxysilane, [3- (diethylamino) propyl] dimethylmethoxysilane, [3- (diethylamino) propyl] diethylmethoxy Silane, [(3-methyl-3-ethylamino) propyl] methyldimethoxysilane, [(3-methyl-3-ethylamino) propyl] ethyldimethoxysilane, [3- (dimethylamino) propyl] methyldiethoxysilane, [3- (Diethylamino) propyl] methyldiethoxysilane, [3- (dimethylamino) propyl] ethyldiethoxysilane, [3- (diethylamino) propyl] ethyldiethoxysilane, [3- (dimethylamino) propyl] dimethyl Ethoxy sila [3- (dimethylamino) propyl] diethylethoxysilane, [3- (diethylamino) propyl] dimethylethoxysilane, [3- (diethylamino) propyl] diethylethoxysilane, [3- (ethylmethylamino) propyl] methyldiethyl Ethoxysilane, [3- (ethylmethylamino) propyl] ethyldiethoxysilane, [3- (benzylmethylamino) propyl] trimethoxysilane, [3- (benzylmethylamino) propyl] triethoxysilane, {3- [ Di (methoxymethyl) amino] propyl} trimethoxysilane, {3- [di (methoxyethyl) amino] propyl} trimethoxysilane, {3- [di (methoxymethyl) amino] propyl} triethoxysilane, {3- [Di (methoxyethyl) amino] propyl} Liethoxysilane, {3- [di (ethoxyethyl) amino] propyl} trimethoxysilane, {3- [di (ethoxymethyl) amino] propyl} trimethoxysilane, {3- [di (ethoxyethyl) amino] propyl ] Triethoxysilane, {3- [di (ethoxymethyl) amino] propyl} triethoxysilane, {3- [N, N-bis (trimethylsilyl) amino] propyl} trimethoxysilane, {3- [N, N- Bis (trimethylsilyl) amino] propyl} triethoxysilane, {3- [N, N-bis (t-butyldimethylsilyl) amino] propyl} trimethoxysilane, {3- [N, N-bis (t-butyldimethyl) [Silyl) amino] propyl} triethoxysilane, {3- [N, N-bis (trimethylsilyl) amino] propyl {Methyldimethoxysilane, {3- [N, N-bis (trimethylsilyl) amino] propyl} methyldiethoxysilane, {3- [N, N-bis (t-butyldimethylsilyl) amino] propyl} methyldimethoxysilane, {3- [N, N-bis (t-butyldimethylsilyl) amino] propyl} methyldiethoxysilane, {3- [N, N-bis (trimethylsilyl) amino] propyl} dimethylmethoxysilane, {3- [N , N-bis (trimethylsilyl) amino] propyl} dimethylethoxysilane, {3- [N, N-bis (t-butyldimethylsilyl) amino] propyl} dimethylmethoxysilane, {N, N-bis- [di (t -Butyldimethylsilyl) amino] propyl} dimethylethoxysilane, [3- (ethylmethylamino) propyl ] Trimethoxysilane, [3- (ethylmethylamino) propyl] triethoxysilane, [3- (ethylmethylamino) propyl] methyldimethoxysilane, [3- (ethylmethylamino) propyl] ethyldimethoxysilane, [3- (Ethylmethylamino) propyl] methyldiethoxysilane and [3- (ethylmethylamino) propyl] ethyldiethoxysilane.

Among the compounds having the structure represented by the formula (6), as a compound in which A ¹ is an acyclic amino group represented by the formula (6-1), from the viewpoint of improving fuel efficiency, [3- ( [Dimethylamino) propyl] trimethoxysilane, [3- (diethylamino) propyl] trimethoxysilane, [3- (dimethylamino) propyl] triethoxysilane or [3- (diethylamino) propyl] triethoxysilane is preferred.

Among the compounds having the structure represented by the formula (6), examples of the compound in which A ¹ is a cyclic amino group represented by the formula (6-1) include, for example, 3-morpholinopropyltrimethoxysilane, 3-morpholinopropyl Triethoxysilane, 3-morpholinopropylmethyldimethoxysilane, 3-morpholinopropylethyldimethoxysilane, 3-morpholinopropylmethyldiethoxysilane, 3-morpholinopropylethyldiethoxysilane, 3-piperidinopropyltrimethoxysilane, 3- Piperidinopropyltriethoxysilane, 3-piperidinopropylmethyldimethoxysilane, 3-piperidinopropylethyldimethoxysilane, 3-piperidinopropylmethyldiethoxysilane, 3-piperidinopropylethyldiethoxysilane, N- (3-trimet (Xysilylpropyl) -4,5-dihydroimidazole, N- (3-triethoxysilylpropyl) -4,5-dihydroimidazole, N- (3-trimethoxysilylpropyl) -4,5-imidazole, N- ( 3-triethoxysilylpropyl) -4,5-imidazole, 3-hexamethyleneiminopropyltrimethoxysilane, 3-hexamethyleneiminopropyltriethoxysilane, 3-hexamethyleneiminopropylmethyldimethoxysilane, 3-hexamethyleneiminopropyl Examples include ethyldimethoxysilane, 3-hexamethyleneiminopropylmethyldiethoxysilane and 3-hexamethyleneiminopropylethyldiethoxysilane.

Among the compounds having the structure represented by the formula (6), as a compound in which A ¹ is a cyclic amino group represented by the formula (6-1), from the viewpoint of improving fuel efficiency, N- (3- Trimethoxysilylpropyl) -4,5-dihydroimidazole, N- (3-triethoxysilylpropyl) -4,5-dihydroimidazole, N- (3-trimethoxysilylpropyl) -4,5-imidazole or N- (3-Triethoxysilylpropyl) -4,5-imidazole is preferred.

Among the compounds having the structure represented by the formula (6), compounds in which A ¹ is a group represented by the formula (6-2) include, for example, 3-glycidoxypropyltrimethoxysilane, 3-glycidyl Examples include: sidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropylethyldiethoxysilane. be able to.

Among the compounds having the structure represented by the formula (6), the compound in which A ¹ is a group represented by the formula (6-2) includes a viewpoint of improving fuel efficiency, availability of the compound, and long-term storage. From the viewpoint of increasing the stability, 3-glycidoxypropyltrimethoxysilane is preferred.

Among the compounds having the structure represented by the formula (6), examples of the compound in which A ¹ is a group represented by the formula (6-3) include, for example, S-trimethylsilylmercaptopropyltrimethoxysilane, S-trimethylsilylmercapto Propyltriethoxysilane, S-trimethylsilylmercaptopropylmethyldimethoxysilane, S-trimethylsilylmercaptopropylmethyldiethoxysilane, S-triethylsilylmercaptopropyltrimethoxysilane, S-triethylsilylmercaptopropyltriethoxysilane, S-triethylsilylmercaptopropyl Examples include methyldimethoxysilane and S-triethylsilylmercaptopropylmethyldiethoxysilane.

Among the compounds having the structure represented by the formula (6), as the compound A ¹ is a group represented by the formula (6-4), for example, diglycide alkoxy polydimethylsiloxane, dimethyl (methoxy - methyl siloxane ) Polydimethylsiloxane, dimethyl (acetoxy-methylsiloxane) polydimethylsiloxane, diglycidyl polysiloxane, dichloropolydimethylsiloxane, and the like.

  Compounds having a structure represented by the formula (6) other than the above compounds include, for example, tris [3- (trimethoxysilyl) propyl] isocyanurate, tris [3- (triethoxysilyl) propyl] isocyanurate, tris Examples include tris [(alkoxysilyl) alkyl] isocyanurate compounds such as [3- (tripropoxysilyl) propyl] isocyanurate and tris [3- (tributoxysilyl) propyl] isocyanurate. Among them, as the compound represented by the formula (6), tris [3- (trialkoxysilyl) propyl] isocyanurate is preferable, and tris [3- (trialkoxy) in which the alkoxy group is an alkoxy group having 1 to 4 carbon atoms. (Silyl) propyl] isocyanurate is more preferred, and tris [3- (trimethoxysilyl) propyl] isocyanurate is still more preferred.

  Compounds having a structure represented by the formula (6) other than the above compounds include, for example, 1,4-bis [3- (trimethoxysilyl) propyl] piperazine, 1,4-bis [3- (triethoxysilyl) ) Propyl] piperazine, bis [3- (trimethoxysilyl) propyl] -N-trimethylsilylamine, bis [3- (triethoxysilyl) propyl] -N-trimethylsilylamine, bis [3- (trimethoxysilyl) propyl] Methylamine, bis [3- (triethoxysilyl) propyl] methylamine, bis [3- (trimethoxysilyl) propyl] ethylamine, bis [3- (triethoxysilyl) propyl] ethylamine, tris (trimethoxysilylmethyl) Amine, tris (triethoxysilylmethyl) amine, 2,2-dimethoxy- -(3-trimethoxysilylpropyl) -1-aza-2-silacyclopentane, 2,2-diethoxy-1- (3-triethoxysilylpropyl) -1-aza-2-silacyclopentane, N- [ 2- (trimethoxysilanyl) -ethyl] -N, N ', N'-trimethylethane-1,2-diamine, 2- [3- (trimethoxysilyl) propyl] -1,3-dimethylimidazolidine and 2- [3- (trimethoxysilyl) propyl] -1,3- (bistrimethylsilyl) imidazolidine.

As the modifier, a compound having a structure represented by the formula (7) can be used. The compound has a functional group copolymerizable with the conjugated diene compound. By polymerizing a monomer containing the compound having the structure represented by the formula (7) together with the conjugated diene compound, a conjugate having a unit based on the compound having the structure represented by the formula (7) in the molecular chain is obtained. A diene polymer can be obtained.

In the formula (7), R ⁷¹ represents a hydrogen atom or a hydrocarbyl group, s represents 0 or 1 (an integer of 0 to 1), R ⁷² represents a hydrocarbylene group, and X ⁷ , X ⁸ and X ⁹ Each independently represents a substituted amino group or a hydrocarbyl group which may have a substituent, and at least one of X ⁷ , X ⁸ and X ⁹ is a substituted amino group.

Examples of the hydrocarbyl group for R ⁷¹ include an alkyl group, an alkenyl group, and an aryl group.
As the alkyl group, an alkyl group having 1 to 12 carbon atoms is preferable, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group and a tert-butyl group. And preferably a methyl group. As the alkenyl group, an alkenyl group having 2 to 12 carbon atoms is preferable, and examples thereof include a vinyl group, an allyl group, a 1-propenyl group and an isopropenyl group, and a vinyl group is preferable. As the aryl group, an aryl group having 6 to 12 carbon atoms is preferable, and examples thereof include a phenyl group, a methylphenyl group, and an ethylphenyl group, and a phenyl group is preferable.
R ⁷¹ is preferably a hydrogen atom, a methyl group, a vinyl group or a phenyl group, and more preferably a hydrogen atom.

Examples of the hydrocarbylene group for R ⁷² include an alkylene group, an arylene group, and a group in which an arylene group and an alkylene group are bonded.
As the alkylene group, an alkylene group having 2 to 6 carbon atoms is preferable, and examples thereof include a methylene group, an ethylene group and a trimethylene group, and preferably a methylene group or an ethylene group. As the arylene group, an arylene group having 5 to 12 carbon atoms is preferable, and examples thereof include a phenylene group, a naphthylene group and a biphenylene group, and a phenylene group is preferable. Examples of the group in which the arylene group and the alkylene group are bonded include, for example, a group in which a phenylene group and an alkylene group are bonded, a group in which a naphthylene group and an alkylene group are bonded, and a group in which a biphenylene group and an alkylene group are bonded. And is preferably a group in which a phenylene group and an alkylene group are bonded.
As the group in which the arylene group and the alkylene group are bonded, it is preferable that the carbon atom of the arylene group of the group be bonded to the carbon atom to which R ⁷¹ of the formula (7) is bonded.

式中、ｄは１〜１０の整数を表す。 Examples of the group in which a phenylene group and an alkylene group are bonded (a phenylene-alkylene group) include a group represented by the formula (7-R).

In the formula, d represents an integer of 1 to 10.

式中、ｄ１、ｄ２及びｄ３はそれぞれ独立に、１〜１０の整数を表す。 Examples of the phenylene-alkylene group include a para-phenylene-alkylene group, a meta-phenylene-alkylene group, and an ortho-phenylene-alkylene group depending on the position of a carbon atom on the benzene ring to which the alkylene group is bonded. In the case of the group represented by the formula (7-R), the para-phenylene-alkylene group is a group represented by the formula (7-Ra), and the meta-phenylene-alkylene group is a group represented by the formula (7-Rb). The ortho-phenylene-alkylene group is a group represented by the formula (7-Rc).

In the formula, d1, d2 and d3 each independently represent an integer of 1 to 10.

  The group in which an arylene group and an alkylene group are bonded is preferably a group in which a phenylene group and an alkylene group are bonded (phenylene-alkylene group), and more preferably a group represented by the formula (7-Ra) Or a group represented by the formula (7-Rb), more preferably a para-phenylene-methylene group (a group represented by the formula (7-Ra) where d1 = 1), and a meta-phenylene-methylene group (A group represented by the formula (7-Rb) where d2 = 1), a para-phenylene-ethylene group (a group represented by the formula (7-Ra) where d1 = 2) or a meta-phenylene-ethylene group (A group represented by the formula (7-Rb) wherein d2 = 2).

Examples of the optionally substituted hydrocarbyl group in X ⁷ , X ⁸ and X ⁹ include a hydrocarbyl group and a substituted hydrocarbyl group.

Examples of the hydrocarbyl group for X ⁷ , X ⁸ and X ⁹ include an alkyl group, an alkenyl group, an alkynyl group, an aryl group and an aralkyl group. As the alkyl group, an alkyl group having 1 to 12 carbon atoms is preferable, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group and a tert-butyl group. Can be. As the alkenyl group, an alkenyl group having 2 to 12 carbon atoms is preferable, and examples thereof include a vinyl group, an allyl group, a 1-propenyl group and an isopropenyl group. As the alkynyl group, an alkynyl group having 2 to 12 carbon atoms is preferable, and examples thereof include an ethynyl group and a 2-propynyl group. As the aryl group, an aryl group having 6 to 12 carbon atoms is preferable, and examples thereof include a phenyl group, a tolyl group, and a xylyl group. The aralkyl group is preferably an aralkyl group having 7 to 13 carbon atoms, and examples thereof include a benzyl group. The hydrocarbyl group is preferably an alkyl group.

Examples of the substituted hydrocarbyl group for X ⁷ , X ⁸ and X ⁹ include groups having at least one atom selected from the group consisting of an oxygen atom, a nitrogen atom and a silicon atom.
Examples of the substituted hydrocarbyl group having an oxygen atom include an alkoxyalkyl group such as a methoxymethyl group, a methoxyethyl group, an ethoxymethyl group, and an ethoxyethyl group.
Examples of the substituted hydrocarbyl group having a nitrogen atom include a dialkylaminoalkyl group such as a dimethylaminomethyl group, a dimethylaminoethyl group, a diethylaminomethyl group, and a diethylaminoethyl group.
Examples of the substituted hydrocarbyl group having a silicon atom include a trialkylsilylalkyl group such as a trimethylsilylmethyl group, a trimethylsilylethyl group, a triethylsilylmethyl group, and a triethylsilylethyl group.

  The number of carbon atoms of the hydrocarbyl group which may have a substituent is preferably 1 to 10, more preferably 1 to 4. The hydrocarbyl group which may have a substituent is preferably an alkyl group or an alkoxyalkyl group. The alkyl group is more preferably an alkyl group having 1 to 4 carbon atoms, and particularly preferably a methyl group or an ethyl group. The alkoxyalkyl group is preferably an alkoxyalkyl group having 2 to 4 carbon atoms.

式（７−Ｘ）中、Ｒ^７３及びＲ^７４はそれぞれ独立に、ヒドロカルビル基又はトリヒドロカルビルシリル基を表すか、あるいは、Ｒ^７３の一部とＲ^７４の一部とが結合して成る、窒素原子及び／又は酸素原子を有していてもよいヒドロカルビレン基を表す。

式（７−Ｙ）中、Ｒ^７５は、ヒドロカルビリデン基を表す。なお、Ｒ^７５は、式（７−Ｘ）において、Ｒ^７３及びＲ^７４が一つの基であって、窒素原子に二重結合で結合する基に対応する基である。 Examples of the substituted amino group for X ⁷ , X ⁸ and X ⁹ include a group represented by the formula (7-X) and a group represented by the formula (7-Y).

In the formula (7-X), R ⁷³ and R ⁷⁴ each independently represent a hydrocarbyl group or a trihydrocarbylsilyl group, or a nitrogen atom formed by combining a part of R ^{73 and} a part of R ^74. Represents a hydrocarbylene group which may have an atom and / or an oxygen atom.

In the formula (7-Y), R ⁷⁵ represents a hydrocarbylidene group. Note that R ⁷⁵ is a group corresponding to a group in which R ⁷³ and R ⁷⁴ are one group in the formula (7-X) and are bonded to a nitrogen atom by a double bond.

Examples of the hydrocarbyl group in R ⁷³ and R ⁷⁴ include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, and an aralkyl group. As the alkyl group, an alkyl group having 1 to 12 carbon atoms is preferable, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group and a tert-butyl group. Can be. As the alkenyl group, an alkenyl group having 2 to 12 carbon atoms is preferable, and examples thereof include a vinyl group, an allyl group, a 1-propenyl group and an isopropenyl group. As the alkynyl group, an alkynyl group having 2 to 12 carbon atoms is preferable, and examples thereof include an ethynyl group and a 2-propynyl group. As the aryl group, an aryl group having 6 to 12 carbon atoms is preferable, and examples thereof include a phenyl group, a tolyl group, and a xylyl group. The aralkyl group is preferably an aralkyl group having 7 to 13 carbon atoms, and examples thereof include a benzyl group.

  The number of carbon atoms of the hydrocarbyl group is preferably 1 to 10, more preferably 1 to 4, and still more preferably 1 to 2. The hydrocarbyl group is preferably an alkyl group, and more preferably a straight-chain alkyl group.

Examples of the trihydrocarbylsilyl group in R ⁷³ and R ⁷⁴ include a trialkylsilyl group having 3 to 12 carbon atoms such as a trimethylsilyl group, a triethylsilyl group, a triisopropylsilyl group, and a tert-butyl-dimethylsilyl group. be able to.

  The trihydrocarbylsilyl group is preferably a trialkylsilyl group having 3 to 9 carbon atoms, more preferably a trialkyl in which the alkyl group bonded to the silicon atom is an alkyl group having 1 to 3 carbon atoms. A silyl group, and more preferably a trimethylsilyl group.

Examples of the hydrocarbylene group optionally having a nitrogen atom and / or an oxygen atom in which a part of ^{R73 and} a part of ^R74 are bonded include, for example, a hydrocarbylene group and a nitrogen atom-containing hydrocarbylene. And hydrocarbylene groups containing oxygen atoms.
Examples of the hydrocarbylene group include an alkylene group such as an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, and a hexamethylene group.
Examples of the nitrogen atom-containing hydrocarbylene group, _{e.g., -CH 2 CH 2 -NH-CH} 2 - , a group represented _by, -CH ₂ CH ₂ -N = CH- group represented by, -CH = CH- N = CH- group represented by and _{-CH 2 CH 2 -NH-CH 2} CH 2 - and the groups represented by.
The oxygen-atom-containing hydrocarbylene group, _{e.g., -CH 2 CH 2 -O-CH} 2 CH 2 - can be mentioned a group represented by.

  The number of carbon atoms of the hydrocarbylene group which may have a nitrogen atom and / or an oxygen atom is preferably 2 to 20, more preferably 2 to 7, and still more preferably 4 to 6.

  The hydrocarbylene group optionally having a nitrogen atom and / or an oxygen atom is preferably a hydrocarbylene group, more preferably an alkylene group, and further preferably a polymethylene group.

R ⁷³ and R ⁷⁴ are preferably each independently an alkyl group or a trialkylsilyl group, or an alkylene group in which a part of R ^{73 and} a part of R ⁷⁴ are bonded, more preferably each independently Is an alkyl group.

  Examples of the group represented by the formula (7-X) include an acyclic amino group and a cyclic amino group.

Among the acyclic amino groups, groups in which R ⁷³ and R ⁷⁴ in Formula (7-X) are hydrocarbyl groups include, for example, a dimethylamino group, a diethylamino group, a di (n-propyl) amino group, and a di (isopropyl) group. Examples thereof include amino groups, di (n-butyl) amino groups, di (sec-butyl) amino groups, di (tert-butyl) amino groups, and dialkylamino groups such as ethylmethylamino group.
Examples of the acyclic amino group in which R ⁷³ and R ⁷⁴ in Formula (7-X) are trihydrocarbylsilyl groups include, for example, a bis (trimethylsilyl) amino group and a bis (tert-butyl-dimethylsilyl) amino group And other bis (trialkylsilyl) amino groups.

Among the cyclic amino groups, in the formula (7-X), examples of the group in which a group in which a part of R ^{73 and} a part of R ⁷⁴ are bonded are a hydrocarbylene group include a 1-aziridinyl group and a 1-aziridinyl group. Examples thereof include an azetidinyl group, a 1-pyrrolidinyl group, a 1-piperidinyl group, a 1-hexamethyleneimino group, and a 1-pyrrolyl group.
Among the cyclic amino groups, in the formula (7-X), examples of the group in which a group in which a part of R ^{73 and} a part of R ⁷⁴ are bonded are a nitrogen atom-containing hydrocarbylene group include a 1-imidazolyl group. , 4,5-dihydro-1-imidazolyl group, 1-imidazolidinyl group and 1-piperazinyl group.
Among the cyclic amino groups, in the formula (7-X), examples of a group in which a part of R ^{73 and} a part of R ⁷⁴ are bonded to each other are an oxygen atom-containing hydrocarbylene group include a morpholino group. it can.

Examples of the hydrocarbylidene group for R ⁷⁵ include an ethylidene group, a propylidene group, a butylidene group, a 1-methylethylidene group, a 1-methylpropylidene group, and a 1,3-dimethylbutylidene group.
The number of carbon atoms of the hydrocarbylidene group is preferably 2 to 20, and more preferably 2 to 6.

  Examples of the group represented by the formula (7-Y) include an ethylideneamino group, a 1-methylpropylideneamino group, a 1,3-dimethylbutylideneamino group, a 1-methylethylideneamino group, a 4-N, N Acyclic amino groups such as -dimethylaminobenzylideneamino group;

In the formula (7), the substituted amino group in X ⁹ , X ⁹ and X ⁹ is preferably an acyclic amino group, more preferably a dialkylamino group, still more preferably a dimethylamino group, a diethylamino group, It is a di (n-propyl) amino group or a di (n-butyl) amino group, particularly preferably a dimethylamino group or a diethylamino group.

In the formula (7), at least one of X ⁷ , X ⁸ and X ⁹ is a substituted amino group, preferably, two or more of X ⁷ , X ⁸ and X ⁹ are a substituted amino group, more preferably , X ⁷ , X ⁸ and X ⁹ are substituted amino groups.

Among the compounds represented by the formula (7), the following compounds can be mentioned as compounds in which R ⁷¹ is a hydrogen atom and one of X ⁷ , X ⁸ and X ⁹ is a dialkylamino group.

  Examples of the compound in which s in Formula (7) is 0 include (dimethylamino) dimethylvinylsilane, (diethylamino) dimethylvinylsilane, (dipropylamino) dimethylvinylsilane, (dibutylamino) dimethylvinylsilane, and (dimethylamino) diethyl. Vinylsilane, (diethylamino) diethylvinylsilane, (dipropylamino) diethylvinylsilane and (dibutylamino) diethylvinylsilane.

  Examples of the compound in which s in the formula (7) is 1 include (dimethylamino) dimethyl (4-vinylphenyl) silane, (dimethylamino) dimethyl (3-vinylphenyl) silane, and (diethylamino) dimethyl (4- (Vinylphenyl) silane, (diethylamino) dimethyl (3-vinylphenyl) silane, (dipropylamino) dimethyl (4-vinylphenyl) silane, (dipropylamino) dimethyl (3-vinylphenyl) silane, (dibutylamino) dimethyl (4-vinylphenyl) silane, (dibutylamino) dimethyl (3-vinylphenyl) silane, (dimethylamino) diethyl (4-vinylphenyl) silane, (dimethylamino) diethyl (3-vinylphenyl) silane, (diethylamino) Diethyl (4-vinylphenyl) silane (Diethylamino) diethyl (3-vinylphenyl) silane, (dipropylamino) diethyl (4-vinylphenyl) silane, (dipropylamino) diethyl (3-vinylphenyl) silane, (dibutylamino) diethyl (4-vinylphenyl) ) Silane and (dibutylamino) diethyl (3-vinylphenyl) silane.

Among the compounds represented by the formula (7), the following compounds can be mentioned as compounds in which R ⁷¹ is a hydrogen atom and two of X ⁷ , X ⁸ and X ⁹ are dialkylamino groups.

  Examples of the compound in which s in Formula (7) is 0 include bis (dimethylamino) methylvinylsilane, bis (diethylamino) methylvinylsilane, bis (dipropylamino) methylvinylsilane, bis (dibutylamino) methylvinylsilane, and bis (dibutylamino) methylvinylsilane. (Dimethylamino) ethylvinylsilane, bis (diethylamino) ethylvinylsilane, bis (dipropylamino) ethylvinylsilane and bis (dibutylamino) ethylvinylsilane.

  Examples of the compound in which s in the formula (7) is 1 include bis (dimethylamino) methyl (4-vinylphenyl) silane, bis (dimethylamino) methyl (3-vinylphenyl) silane, and bis (diethylamino) methyl (4-vinylphenyl) silane, bis (diethylamino) methyl (3-vinylphenyl) silane, bis (dipropylamino) methyl (4-vinylphenyl) silane, bis (dipropylamino) methyl (3-vinylphenyl) silane , Bis (dibutylamino) methyl (4-vinylphenyl) silane, bis (dibutylamino) methyl (3-vinylphenyl) silane, bis (dimethylamino) ethyl (4-vinylphenyl) silane, bis (dimethylamino) ethyl ( 3-vinylphenyl) silane, bis (diethylamino) ethyl (4- Nilphenyl) silane, bis (diethylamino) ethyl (3-vinylphenyl) silane, bis (dipropylamino) ethyl (4-vinylphenyl) silane, bis (dipropylamino) ethyl (3-vinylphenyl) silane, bis (dibutyl) Amino) ethyl (4-vinylphenyl) silane and bis (dibutylamino) ethyl (3-vinylphenyl) silane.

Among the compounds represented by the formula (7), the following compounds can be mentioned as compounds in which R ⁷¹ is a methyl group and two of X ⁷ , X ⁸ and X ⁹ are dialkylamino groups.

  Examples of the compound in which s in the formula (7) is 1 include bis (dimethylamino) methyl (4-isopropenylphenyl) silane, bis (dimethylamino) methyl (3-isopropenylphenyl) silane, bis (diethylamino) ) Methyl (4-isopropenylphenyl) silane, bis (diethylamino) methyl (3-isopropenylphenyl) silane, bis (dipropylamino) methyl (4-isopropenylphenyl) silane, bis (dipropylamino) methyl (3 -Isopropenylphenyl) silane, bis (dibutylamino) methyl (4-isopropenylphenyl) silane, bis (dibutylamino) methyl (3-isopropenylphenyl) silane, bis (dimethylamino) ethyl (4-isopropenylphenyl) Silane, bis (dimethylamino Ethyl (3-isopropenylphenyl) silane, bis (diethylamino) ethyl (4-isopropenylphenyl) silane, bis (diethylamino) ethyl (3-isopropenylphenyl) silane, bis (dipropylamino) ethyl (4-isopropenyl) Phenyl) silane, bis (dipropylamino) ethyl (3-isopropenylphenyl) silane, bis (dibutylamino) ethyl (4-isopropenylphenyl) silane and bis (dibutylamino) ethyl (3-isopropenylphenyl) silane No.

Examples of the compound represented by the formula (7) include the following compounds as compounds in which R ⁷¹ is a vinyl group and two of X ⁷ , X ⁸ and X ⁹ are dialkylamino groups.

  Examples of the compound in which s in Formula (7) is 0 include bis (dimethylamino) methyl (1-methylene-2-propenyl) silane, bis (diethylamino) methyl (1-methylene-2-propenyl) silane, Bis (dipropylamino) methyl (1-methylene-2-propenyl) silane, bis (dibutylamino) methyl (1-methylene-2-propenyl) silane, bis (dimethylamino) ethyl (1-methylene-2-propenyl) Silane, bis (diethylamino) ethyl (1-methylene-2-propenyl) silane, bis (dipropylamino) ethyl (1-methylene-2-propenyl) silane and bis (dibutylamino) ethyl (1-methylene-2-propenyl) ) Silane.

Examples of the compound represented by the formula (7) include the following compounds as compounds in which R ⁷¹ is a phenyl group and two of X ⁷ , X ⁸ and X ⁹ are dialkylamino groups.

  Examples of the compound in which s in the formula (7) is 1 include 1- {4- [bis (dimethylamino) methylsilyl] phenyl} -1-phenylethylene and 1- {4- [bis (diethylamino) methylsilyl] Phenyl} -1-phenylethylene, 1- {4- [bis (dipropylamino) methylsilyl] phenyl} -1-phenylethylene, 1- {4- [bis (dibutylamino) methylsilyl] phenyl} -1-phenylethylene , 1- {4- [bis (dimethylamino) ethylsilyl] phenyl} -1-phenylethylene, 1- {4- [bis (diethylamino) ethylsilyl] phenyl} -1-phenylethylene, 1- {4- [bis ( Dipropylamino) ethylsilyl] phenyl} -1-phenylethylene and 1- {4- [bis (dibutylamino) ethyl Silyl] phenyl} -1-phenyl ethylene.

Examples of the compound represented by the formula (7) include the following compounds as compounds in which R ⁷¹ is a hydrogen atom and three of X ⁷ , X ⁸ and X ⁹ are dialkylamino groups.

  Examples of the compound in which s in Formula (7) is 0 include tris (dimethylamino) vinylsilane, tris (diethylamino) vinylsilane, tris (dipropylamino) vinylsilane, and tris (dibutylamino) vinylsilane.

  Examples of the compound in which s in Formula (7) is 1 include tris (dimethylamino) (4-vinylphenyl) silane, tris (dimethylamino) (3-vinylphenyl) silane, and tris (diethylamino) (4- Vinylphenyl) silane, tris (diethylamino) (3-vinylphenyl) silane, tris (dipropylamino) (4-vinylphenyl) silane, tris (dipropylamino) (3-vinylphenyl) silane, tris (dibutylamino) (4-vinylphenyl) silane and tris (dibutylamino) (3-vinylphenyl) silane.

Examples of the compound represented by the formula (7) include the following compounds as compounds in which R ⁷¹ is a methyl group and three of X ⁷ , X ⁸ and X ⁹ are dialkylamino groups.
Examples of the compound in which s in the formula (7) is 1 include, for example, tris (dimethylamino) (4-isopropenylphenyl) silane, tris (dimethylamino) (3-isopropenylphenyl) silane, tris (diethylamino) ( 4-isopropenylphenyl) silane, tris (diethylamino) (3-isopropenylphenyl) silane, tris (dipropylamino) (4-isopropenylphenyl) silane, tris (dipropylamino) (3-isopropenylphenyl) silane , Tris (dibutylamino) (4-isopropenylphenyl) silane and tris (dibutylamino) (3-isopropenylphenyl) silane.

Examples of the compound represented by the formula (7) include the following compounds as compounds in which R ⁷¹ is a vinyl group and three of X ⁷ , X ⁸ and X ⁹ are dialkylamino groups.

  Examples of the compound in which s in Formula (7) is 0 include tris (dimethylamino) (1-methylene-2-propenyl) silane, tris (diethylamino) (1-methylene-2-propenyl) silane, tris ( Dipropylamino) (1-methylene-2-propenyl) silane and tris (dibutylamino) (1-methylene-2-propenyl) silane.

Examples of the compound represented by the formula (7) include the following compounds as compounds in which R ⁷¹ is a phenyl group and three of X ⁷ , X ⁸ and X ⁹ are dialkylamino groups.

  Compounds in which s in the formula (7) is 1 include, for example, 1- [4-tris (dimethylamino) silylphenyl] -1-phenylethylene, 1- [4-tris (diethylamino) silylphenyl] -1 -Phenylethylene, 1- [4-tris (di-n-propylamino) methylsilylphenyl] -1-phenylethylene and 1- [4-tris (di-n-butylamino) methylsilylphenyl] -1-phenyl Ethylene.

The compound represented by the formula (7) is preferably a compound in which two of X ⁷ , X ⁸ and X ^{9 in} the formula (7) are a dialkylamino group, and more preferably a compound represented by the formula (7) A compound in which two of X ⁷ , X ⁸ and X ⁹ are a dialkylamino group, R ⁷¹ is a hydrogen atom, and s is 0.

  Most preferably, the compound represented by the formula (7) is bis (dimethylamino) methylvinylsilane, bis (diethylamino) methylvinylsilane, bis (dipropylamino) methylvinylsilane, bis (dibutylamino) methylvinylsilane, bis (dimethylamino) ) Ethylvinylsilane, bis (diethylamino) ethylvinylsilane, bis (dipropylamino) ethylvinylsilane, and bis (dibutylamino) ethylvinylsilane.

  The modified conjugated diene-based polymer of the present embodiment can be obtained by reacting a monomer containing a conjugated diene compound in a hydrocarbon solvent.

  In the terminal and / or in the molecular chain of the modified conjugated diene-based polymer, a unit based on a compound having a silicon atom as a modifier can be introduced. When a unit based on a modifier is introduced into the molecular chain of the polymer, a compound having a functional group copolymerizable with a conjugated diene compound (for example, a compound represented by the formula (7)) may be used as the compound having a silicon atom. ) Can be used as a monomer. That is, the modified conjugated diene-based polymer is obtained by copolymerizing a monomer containing a conjugated diene compound and a compound having a functional group copolymerizable with the conjugated diene compound in a hydrocarbon solvent in the presence of a polymerization initiator. Can be obtained.

  When a unit based on a modifier is introduced into the terminal of the conjugated diene-based polymer, a compound having a functional group capable of reacting with the active terminal of the polymer (for example, represented by the formula (6)) Compound). In this case, the modified conjugated diene-based polymer may be produced by the following method.

  First, a monomer containing a conjugated diene compound is polymerized in a hydrocarbon solvent in the presence of a polymerization initiator to obtain a polymer having an active terminal. Next, the polymer is reacted with a silicon compound having a functional group capable of reacting with the active terminal of the polymer to introduce a unit based on the compound having a silicon atom at the terminal of the polymer.

  The method for producing a modified conjugated diene-based polymer according to the present embodiment includes a step of reacting a monomer containing a conjugated diene compound in a hydrocarbon solvent to obtain a conjugated diene-based polymer; Reacting with a compound having a silicon atom to obtain a modified conjugated diene-based polymer having a unit based on the compound having a silicon atom at a terminal.

  Further, a silicon compound having a functional group copolymerizable with a conjugated diene compound and a silicon compound having a functional group capable of reacting with the active terminal of the polymer are used in combination, and a silicon atom is present in the molecular chain and at the terminal of the polymer. A unit based on a compound having the formula:

  The modified conjugated diene-based polymer is obtained by a known recovery method, for example, a method of adding a coagulant to a hydrocarbon solution of the modified conjugated diene-based polymer, or a method of adding steam to a hydrocarbon solution of the modified conjugated diene-based polymer. Can be recovered from a hydrocarbon solution of the modified conjugated diene polymer. The recovered modified conjugated diene-based polymer may be dried by a known dryer such as a band dryer and an extrusion dryer. Further, in order to improve the processability of the acid-modified conjugated diene-based polymer, before separating the solvent from the polymerization solution of the modified conjugated diene-based polymer, add an extender oil to the solution, the modified conjugated diene-based polymer May be collected as oil-extended rubber.

  Preparation of the modified conjugated diene-based polymer is an agent for adjusting the vinyl bond amount of the monomer unit derived from the conjugated diene compound, the monomer unit derived from the conjugated diene compound in the modified conjugated diene-based polymer chain And an agent for adjusting the distribution of the monomer units derived from the aromatic vinyl compound and the monomer units derived from the other compounds (hereinafter, collectively referred to as "regulator"). Is also good.

  As a regulator, an ether compound, a tertiary amine, a phosphine compound, an alkali metal alkoxide, an alkali metal phenoxide, or the like can be used. Examples of the ether compound include cyclic ethers such as tetrahydrofuran, tetrahydropyran, 1,4-dioxane, and 2,2-di (tetrahydrofuryl) propane; aliphatic monoethers such as diethyl ether and dibutyl ether; ethylene glycol dimethyl ether; Aliphatic diethers such as ethylene glycol diethyl ether and ethylene glycol dibutyl ether; aliphatic triethers such as diethylene glycol diethyl ether and diethylene glycol dibutyl ether; aromatics such as diphenyl ether, anisole, 1,2-dimethoxybenzene and 3,4-dimethoxytoluene Ethers. Examples of the tertiary amine include triethylamine, tripropylamine, tributylamine, 1,1,2,2-tetramethylethylenediamine, N, N-diethylaniline, pyridine and quinoline. Examples of the phosphine compound include trimethylphosphine, triethylphosphine, and triphenylphosphine. Examples of the alkali metal alkoxide include sodium-tert-butoxide, potassium-tert-butoxide, sodium-tert-pentoxide and potassium-tert-pentoxide. Examples of the alkali metal phenoxide include sodium phenoxide and potassium phenoxide. These may be used alone or in combination of two or more.

  When producing the modified conjugated diene-based polymer according to the present embodiment, a coupling agent may be added to the polymerization solution from the start of the polymerization of the monomer to the termination of the polymerization.

  As the coupling agent, for example, silicon tetrachloride, methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, tin tetrachloride, methyltrichlorotin, dimethyldichlorotin, trimethylchlorotin, tetramethoxysilane, methyltrimethoxysilane, dimethoxydimethyl Examples include silane, methyltriethoxysilane, ethyltrimethoxysilane, dimethoxydiethylsilane, diethoxydimethylsilane, tetraethoxysilane, ethyltriethoxysilane and diethoxydiethylsilane.

  The amount of the coupling agent to be added is not particularly limited, but when the polymerization initiator contains an alkali metal, preferably 0.03 mol per 1 mol of the alkali metal in order to enhance the cold flow resistance of the conjugated diene-based polymer to be produced. Or more, more preferably 0.05 mol or more. Further, the addition amount of the coupling agent is preferably 0.4 mol or less, more preferably 0.3 mol or less per 1 mol of alkali metal, in order to enhance the fuel efficiency of the acid-modified conjugated diene-based polymer composition. is there.

  The weight-average molecular weight (Mw) of the modified conjugated diene-based polymer according to the present embodiment is preferably from 80,000 to 1200,000, more preferably from 85,000 to 800,000, and still more preferably from 85,000 to 8,000, in order to increase the tensile strength at break. 500,000. The molecular weight distribution of the conjugated diene-based polymer is preferably from 1 to 5, more preferably from 1 to 2, in order to enhance fuel economy. The molecular weight distribution can be determined by measuring the number average molecular weight (Mn) and Mw by gel permeation chromatography (GPC), and dividing Mw by Mn. Mw and Mn can be measured by, for example, a GPC apparatus “HLC-8020” manufactured by Tosoh Corporation. As the column, for example, “GMH-XL” manufactured by Tosoh Corporation can be used. As the molecular weight standard substance, for example, standard polystyrene manufactured by Tosoh Corporation can be used.

The Mooney viscosity (ML _{1 + 4} ) of the modified conjugated diene polymer is preferably 10 or more, more preferably 20 or more, in order to increase the tensile strength at break. Further, the Mooney viscosity of the modified conjugated diene polymer is preferably 200 or less, more preferably 150 or less, in order to enhance processability. Mooney viscosity (ML _{1 + 4} ) is measured at 100 ° C. according to JIS K6300-1 (2013).

The vinyl bond amount of the modified conjugated diene-based polymer is preferably 80 mol% or less, more preferably 70 mol%, with the content of the monomer unit derived from the conjugated diene compound being 100 mol% to improve fuel efficiency. % Or less. Further, the amount of vinyl bond of the modified conjugated diene-based polymer is preferably 10 mol% or more, more preferably 10 mol% or more, with the content of the monomer unit derived from the conjugated diene compound being 100 mol%, in order to enhance grip properties. It is at least 15 mol%, more preferably at least 20 mol%, particularly preferably at least 30 mol%. The vinyl bond amount is determined from the absorption intensity near 910 cm ^−1, which is the absorption peak of the vinyl group, by infrared spectroscopy.

[Acid-modified conjugated diene polymer composition]
The acid-modified conjugated diene-based polymer composition of the present embodiment contains a modified conjugated diene-based polymer having a silicon atom and a compound derived from an organic acid, and is stored at 100 ° C. for 2 weeks in a 50 ° C. constant temperature bath. Of the Mooney viscosity ML (1 + 4) at 100 ° C. is 10 or less.

  The acid-modified conjugated diene-based polymer according to the present embodiment can be obtained by the above-described production method. For example, when the modified conjugated diene-based polymer has a hydrolyzable alkoxysilyl group, the acid-modified conjugated diene-based polymer has a unit in which the alkoxysilyl group is hydrolyzed.

  The compound derived from an organic acid according to this embodiment may be the above-described organic acid, or may be a compound derived from the organic acid when preparing the polymer composition.

  In order to sufficiently suppress the cold flow, the polymer composition according to the present embodiment preferably has a Mooney viscosity change width (ΔML) at 100 ° C. when stored at 50 ° C. for 2 weeks of preferably 5 or less, It is more preferably 4 or less, and further preferably 3 or less. ΔML can be determined from the Mooney viscosity of the initial polymer composition and the Mooney viscosity measured after storing the initial polymer composition in a thermostat at 50 ° C. for 2 weeks.

  The content of the compound derived from an organic acid is preferably more than 0.2 parts by mass, based on 100 parts by mass of the acid-modified conjugated diene-based polymer, since the cold flow of the polymer composition is more suppressed. Preferably it is 0.25-5 mass parts, More preferably, it is 0.3-4 mass parts.

  The polymer composition according to the present embodiment may include a reinforcing material. Examples of the reinforcing material include silica, calcium silicate, aluminum silicate, aluminum hydroxide, and carbon black. The reinforcing materials may be used alone or in combination of two or more.

Examples of the silica include dry silica (silicic anhydride), wet silica (hydrous silicic acid), colloidal silica, and precipitated silica. BET specific surface area of silica is ^{preferably, 50m 2 / g~250m 2 / g} . The BET specific surface area is measured according to ASTM D1993-3. Commercially available silica products include “Ultrasil VN3GR”, “Ultrasil 7000GR”, “Ultrasil 9100GR” and “Ultrasil 5000GR” manufactured by Evonik, and “VN3” and “AQ” manufactured by Tosoh Silica. , "ER", "RS-150", trade names "Zeosil 1115MP", "Zeosil 1165MP" manufactured by Solvay, and the like. Silica may be used alone or in combination of two or more.

  Examples of the carbon black include furnace black, acetylene black, thermal black, channel black, and graphite. Examples of the channel black include EPC, MPC, and CC. Examples of the furnace carbon black include SAF, ISAF, HAF, MAF, FEF, SRF, GPF, APF, FF, CF, SCF and ECF. Examples of the thermal black include FT and MT. The carbon blacks may be used alone or in combination of two or more.

Nitrogen adsorption specific surface area _(N 2 SA) of carbon black is ^{preferably, 5m 2 / g~200m 2 / g} . The absorption amount of dibutyl phthalate (DBP) of carbon black is preferably 5 mL / 100 g to 300 mL / 100 g. The nitrogen adsorption specific surface area can be measured according to ASTM D4820-93, and the DBP absorption can be measured according to ASTM D2414-93. Commercial products of carbon black include “Diablack N339” (trade name, manufactured by Mitsubishi Chemical Corporation), “Seast 6,” “Seam 7HM,” “Seast KH” (trade names, manufactured by Tokai Carbon Co., Ltd.), and Orion Engineered Carbons. Brand name "CK 3", "Special Black 4A", or the like.

  The content of the reinforcing material in the polymer composition is preferably 10 to 150 parts by mass with respect to 100 parts by mass of the polymer. In addition, the amount is more preferably 20 parts by mass or more, and further preferably 30 parts by mass or more, in order to enhance abrasion resistance and strength. Further, the content of the reinforcing material is more preferably 120 parts by mass or less, and further preferably 100 parts by mass or less, in order to enhance the reinforcing property.

  The polymer composition according to the present embodiment may further contain other polymer components, additives, and the like.

  As other polymer components, for example, conventional styrene-butadiene copolymer rubber, polybutadiene rubber, butadiene-isoprene copolymer rubber, butyl rubber, natural rubber, ethylene-propylene copolymer and ethylene-octene copolymer No. These polymer components may be used alone or in combination of two or more.

  When another polymer component is blended, the content of the acid-modified conjugated diene-based polymer according to the present embodiment in the polymer composition is determined based on the total amount of the polymer component (acid-modified conjugated diene) from the viewpoint of enhancing wet grip performance. The amount is preferably 10 parts by mass or more, more preferably 20 parts by mass or more, based on 100 parts by mass (including a system polymer).

  Known additives can be used as the additives, and vulcanizing agents such as sulfur; thiazole vulcanization accelerators, thiuram vulcanization accelerators, sulfenamide vulcanization accelerators, and guanidine vulcanization accelerators. Vulcanization accelerators such as stearic acid and zinc oxide; organic peroxides such as dicumyl peroxide and di-tert-butyl peroxide; calcium carbonate, talc, alumina, clay and hydroxide Fillers such as aluminum and mica; silane coupling agents; extender oils; processing aids; antioxidants; and lubricants.

  Examples of the silane coupling agent include vinyltrichlorosilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxy Silane, γ-methacryloxypropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, N-phenyl-γ -Aminopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, bis (3- (triethoxysilyl) propyl) disulfide, bis (3- (tri Ethoxysilyl Propyl) tetrasulfide, .gamma.-trimethoxysilylpropyl dimethylthiocarbamoyl tetrasulfide and .gamma.-trimethoxysilylpropyl benzothiazyl tetrasulfide and the like. The silane coupling agents may be used alone or in combination of two or more. Commercially available products such as "Si69" and "Si75" (trade names, manufactured by Evonik Corporation) can be used.

  The amount of the silane coupling agent is preferably 1 to 20 parts by mass, more preferably 2 to 15 parts by mass, and still more preferably 5 to 10 parts by mass with respect to 100 parts by mass of the reinforcing material.

  Examples of the extender oil include an aromatic mineral oil (viscosity constant (VGC value) 0.900 to 1.049) and a naphthenic mineral oil (VGGC value 0.850). -0.899) and paraffinic mineral oil (VGC value 0.790-0.849). The polycyclic aromatic content of the extender oil is preferably less than 3% by weight, more preferably less than 1% by weight. The polycyclic aromatic content is measured according to the British Petroleum Institute 346/92 method. The aromatic compound content (CA) of the extender oil is preferably at least 20% by mass. Extending oils may be used alone or in combination of two or more.

  Examples of the sulfur include powdered sulfur, precipitated sulfur, colloidal sulfur, insoluble sulfur, and highly dispersible sulfur. The amount of sulfur is preferably 0.1 to 15 parts by mass, more preferably 0.3 to 10 parts by mass, and still more preferably 0.5 to 5 parts by mass, based on 100 parts by mass of the polymer component. Department.

  Examples of the vulcanization accelerator include thiazole vulcanization accelerators such as 2-mercaptobenzothiazole, dibenzothiazyl disulfide, and N-cyclohexyl-2-benzothiazylsulfenamide; tetramethylthiuram monosulfide, tetramethyl Thiuram-based vulcanization accelerators such as thiuram disulfide; N-cyclohexyl-2-benzothiazolesulfenamide, Nt-butyl-2-benzothiazolesulfenamide, N-oxyethylene-2-benzothiazolesulfenamide; Sulfenamide-based vulcanization accelerators such as N-oxyethylene-2-benzothiazolesulfenamide and N, N'-diisopropyl-2-benzothiazolesulfenamide; diphenylguanidine, dioltotolylguanidine, orthotolylbiguanidine etc Guanidine-based vulcanization accelerator and the like. The vulcanization accelerators may be used alone or in combination of two or more. The compounding amount of the vulcanization accelerator is preferably 0.1 to 5 parts by mass, more preferably 0.2 to 3 parts by mass, based on 100 parts by mass of the polymer component.

  The composition containing the vulcanizing agent and the vulcanization accelerator can be usually used as a vulcanized sheet after vulcanization such as press vulcanization. The vulcanization temperature is usually 120 to 200C, preferably 140 to 180C.

  The polymer composition according to the present embodiment has a small change with time in viscosity during storage and is excellent in cold flow resistance. The polymer composition can be used for tires, shoe soles, flooring materials, vibration insulators, etc., and is particularly preferably used for tires.

  Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.

  Physical properties were evaluated by the following methods.

1. Styrene unit content (unit: mass%)
According to JIS K 6383 (2001), the content of the monomer unit derived from styrene of the polymer was determined from the refractive index.

2. Vinyl bond amount (unit: mol%)
The amount of vinyl bonds in the polymer was determined by infrared spectroscopy from the absorption intensity near 910 cm ^−1, which is the absorption peak of the vinyl group.

3. Molecular weight distribution (Mw)
The Mw of the polymer was measured by the gel permeation chromatography (GPC) method under the following conditions (1) to (8).
(1) Apparatus: Tosoh HLC-8220
(2) Separation column: TSKgel SuperHM-H manufactured by Tosoh Corporation (two in series)
(3) Measurement temperature: 40 ° C
(4) Carrier: tetrahydrofuran (5) Flow rate: 0.6 mL / min (6) Injection volume: 5 μL
(7) Detector: Differential refraction (8) Molecular weight standard: Standard polystyrene

4. Mooney viscosity (ML (1 + 4))
According to JIS K6300-1 (2013), the Mooney viscosity of the polymer composition (the Mooney viscosity before storage) was measured at 100 ° C. within 3 hours after preparing the polymer composition. Next, the Mooney viscosity was measured after storing the polymer composition in a thermostat at 50 ° C. for 2 weeks. The change width (ΔML) of Mooney viscosity was calculated according to the following equation.
ΔML = (Mooney viscosity after storage) − (Mooney viscosity before storage)
In addition, the Mooney viscosity of the polymer composition was measured within 24 hours before preparing a compound using the polymer composition. Next, the compound Mooney viscosity was measured within 6 hours after preparing the compound using the polymer composition. It can be said that the lower the compound Mooney viscosity, the better the workability.

5. Cold flow test Within 3 hours after preparing the polymer composition, the polymer composition was press-formed at 100 ° C. for 20 minutes to prepare a cylindrical test piece having a diameter of 29 mm and a height of 25 mm. The test piece was stored in an oven heated to 40 ° C., the height of the test piece after 7 days had elapsed was measured, and the height retention was determined by the following formula.
Height retention rate (%) = (Test piece height after 7 days / Test piece height before test) × 100

6. Wet grip characteristics A strip-shaped test piece having a width of 1 mm or 2 mm and a length of 40 mm was punched out from a sheet-shaped vulcanized molded product and used for the test. In the measurement, the loss tangent (tan δ (0 ° C.)) of the test piece at a temperature of 0 ° C. was measured by a viscoelasticity measuring device (manufactured by Kamishima Seisakusho) under the conditions of a strain of 2.5% and a frequency of 10 Hz. The larger the value, the better the wet grip performance.

7. Fuel Economy A strip-shaped test piece having a width of 1 mm or 2 mm and a length of 40 mm was punched from a sheet-shaped vulcanized molded product and used for the test. For the measurement, the loss tangent (tan δ (70 ° C.)) of the test piece at a temperature of 70 ° C. was measured by a viscoelasticity measuring device (manufactured by Kamishima Seisakusho) under the conditions of a strain of 1% and a frequency of 10 Hz. The smaller the value, the better the fuel economy.

[Example 1]
(Modified conjugated diene polymer)
The inside of a 20 L stainless steel polymerization reactor equipped with a stirrer was purged with dry nitrogen. Next, 10.2 kg of industrial hexane (trade name: Hexane (general product), manufactured by Sumitomo Chemical Co., Ltd., density: 0.68 g / mL), 720 g of 1,3-butadiene, 80 g of styrene, 6.07 mL of tetrahydrofuran, and ethylene glycol 0.75 mL of diethyl ether was charged into the polymerization reactor. Next, an n-hexane solution containing 13.33 mmol of n-butyllithium (n-BuLi) was charged into the polymerization reactor, and the mixture was stirred at a stirring speed of 130 rpm and a temperature of 65 ° C in the polymerization reactor. .

  While continuously supplying 1080 g of 1,3-butadiene and 120 g of styrene to the above mixture, the mixture was further stirred for 2.5 hours under the above conditions to obtain a polymerization solution. Next, to the obtained polymerization solution, 13.33 mmol of [3- (diethylamino) propyl] trimethoxysilane was added, and the mixture was stirred for 15 minutes. Then, 20 mL of a hexane solution containing 0.81 mL of methanol was added, and the polymerization solution was further added. The mixture was stirred for 5 minutes to obtain a polymerization solution a1.

  8.0 g of 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenylacrylate (Sumitomo Chemical Co., Ltd., trade name: Sumilizer GM) was added to the polymerization solution a1. And 4.0 g of pentaerythrityltetrakis (3-laurylthiopropionate) (manufactured by Sumitomo Chemical Co., Ltd., trade name: Sumilizer TP-D) to obtain a polymerization solution a2 containing the modified conjugated diene polymer A.

(Polymer composition)
To a polymerization solution a2 containing 300 g of the modified conjugated diene-based polymer A, 50 mL of a THF solution containing 6.0 g of stearic acid was added, and the mixture was stirred, spread out in a vat, allowed to stand at room temperature for 12 hours, and dried at 65 ° C. Heat treatment was performed for 6.5 hours under reduced pressure to obtain a polymer composition.

[Example 2]
A polymer composition was prepared in the same manner as in Example 1 except that the amount of stearic acid was changed to 3.0 g.

[Example 3]
A polymer composition was prepared in the same manner as in Example 1 except that the amount of stearic acid was changed to 2.1 g.
[Example 4]
A polymer composition was prepared in the same manner as in Example 1 except that the amount of stearic acid was changed to 1.2 g.

[Comparative Example 1]
A modified conjugated diene polymer composition was prepared in the same manner as in Example 1 except that stearic acid was not added.

  Styrene unit content, vinyl bond content and Mw of the modified conjugated diene-based polymer A in Examples 1 to 4 and Comparative Example 1, content of organic acid with respect to 100 parts by mass of the modified conjugated diene-based polymer A, polymer composition Table 1 shows the heat treatment conditions, ΔML, and cold flow test results.

[Example 5]
(Modified conjugated diene polymer)
The inside of a 20 L stainless steel polymerization reactor equipped with a stirrer was purged with dry nitrogen. Next, 7.7 kg of industrial hexane, 608 g of 1,3-butadiene, 192 g of styrene, 4.56 mL of tetrahydrofuran, and 3.28 mL of ethylene glycol diethyl ether were charged into the polymerization reactor. Next, an n-hexane solution containing 13.70 mmol of n-BuLi was charged into the polymerization reactor, and the mixture was stirred at a stirring speed of 130 rpm and a temperature of 65 ° C in the polymerization reactor.

  While continuously supplying 912 g of 1,3-butadiene and 288 g of styrene to the above mixture, the mixture was further stirred for 3 hours under the above conditions, and then an n-hexane solution containing 0.21 mmol of silicon tetrachloride was added. 1.60 mL was charged into the polymerization reactor and stirred for 15 minutes to obtain a polymerization solution. Next, after adding 11.51 mmol of [3- (diethylamino) propyl] trimethoxysilane to the obtained polymerization solution and stirring for 15 minutes, 20 mL of a hexane solution containing 0.85 mL of methanol was added, and the polymerization solution was further added. The mixture was stirred for 5 minutes to obtain a polymerization solution b1.

  8.0 g of "SUMILIZER GM" and 4.0 g of "SUMILIZER TP-D" were added to the polymerization solution b1, to obtain a polymerization solution b2 containing the modified conjugated diene-based polymer B.

(Polymer composition)
To a polymerization solution b2 containing 600 g of the modified conjugated diene-based polymer B, 50 mL of a THF solution containing 6.0 g of stearic acid was added, and the mixture was stirred, spread out in a vat, left standing at room temperature for 12 hours, and dried at 65 ° C. Heat treatment was carried out for 6.5 hours while reducing the pressure to prepare a polymer composition.

(Vulcanized sheet)
80.0 parts by mass of silica (trade name: Ultrasil VN3GR, manufactured by Evonik), 6.4 parts by mass of silane coupling agent (trade name: Si69, manufactured by Evonik), 100 parts by mass of the polymer composition, carbon 5.0 parts by mass of black (manufactured by Mitsubishi Chemical Corporation, trade name: Diamond Black N339), 40.0 parts by mass of extension oil (manufactured by Japan Energy Co., Ltd., trade name: JOMO Process NC-140), antiaging agent (Sumitomo Chemical Co., Ltd.) 2.0 parts by mass, wax (manufactured by Ouchi Shinko Chemical Co., Ltd., trade name: Sunnock N), 2.0 parts by mass, wax (manufactured by Stractol, trade name: EF44) 0 parts by mass and 3.0 parts by mass of zinc white were added, and kneaded with a Labo Plastomill to prepare a polymer composition.

  Subsequently, 1.5 parts by mass of a vulcanization accelerator (trade name: Succinol CZ, manufactured by Sumitomo Chemical Co., Ltd.) and 241 parts by mass of the polymer composition, 2 vulcanization accelerators (trade name: Succinol D, manufactured by Sumitomo Chemical Co., Ltd.) 0.0 parts by mass and 1.5 parts by mass of sulfur were added, and a compound was formed into a sheet by a 6-inch roll. The compound was heated at 160 ° C. for 55 minutes for vulcanization to prepare a vulcanized sheet.

[Comparative Example 2]
Except that stearic acid was not added, a polymer composition, a compound and a vulcanized sheet were produced in the same manner as in Example 5.

  Styrene unit content, vinyl bond content and Mw of the modified conjugated diene-based polymer B in Example 5 and Comparative Example 2, content of organic acid with respect to 100 parts by mass of the modified conjugated diene-based polymer B, heat treatment of the polymer composition Table 2 shows the results of the conditions, Mooney viscosity, wet grip properties, and fuel economy. The wet grip property and the fuel saving property in Table 2 are relative values with Example 5 being 100.

[Example 6]
(Modified conjugated diene polymer)
The inside of a 30 L stainless steel polymerization reactor equipped with a stirrer was purged with dry nitrogen. Next, 12.2 kg of industrial hexane, 3.51 kg of cyclohexane, 900 g of 1,3-butadiene, 300 g of styrene, 9.10 mL of tetrahydrofuran, and 6.53 mL of ethylene glycol diethyl ether were charged into the polymerization reactor. Next, an n-hexane solution containing 19.48 mmol of n-BuLi was charged into the polymerization reactor, and the mixture was stirred at a stirring speed of 130 rpm and a temperature of 65 ° C in the polymerization reactor.

  While continuously supplying 1350 g of 1,3-butadiene and 450 g of styrene to the mixture, the mixture was further stirred for 2.5 hours under the above conditions to obtain a polymerization solution. Next, after adding 19.48 mmol of [3- (diethylamino) propyl] trimethoxysilane to the obtained polymerization solution and stirring for 15 minutes, 20 mL of a hexane solution containing 1.18 mL of methanol was added, and the polymerization solution was further added. The mixture was stirred for 5 minutes to obtain a polymerization solution c1.

  12.0 g of "SUMILIZER GM" and 6.0 g of "SUMILIZER TP-D" were added to the polymerization solution c1 to obtain a polymerization solution c2 containing the modified conjugated diene-based polymer C. Next, the polymerization solution c2 was spread on a vat, allowed to stand at room temperature for 12 hours, and then heat-treated under reduced pressure at 65 ° C for 6.5 hours to prepare a modified conjugated diene-based polymer C.

(Polymer composition)
40 g of the modified conjugated diene-based polymer C was charged into a Labo Plastomill having an internal capacity of 60 mL and masticated, and the resin temperature was set to 150 ° C. Next, 0.12 g of stearic acid was put into Labo Plastomill, and the modified conjugated diene polymer C and stearic acid were kneaded at 150 ° C. for 1 minute to obtain a polymer composition.

[Comparative Example 3]
A polymer composition was obtained in the same manner as in Example 6, except that the resin temperature was changed to 30 ° C.

[Example 7]
40 g of the modified conjugated diene-based polymer C was charged into a Labo Plastomill having an internal capacity of 60 mL and masticated, and the resin temperature was set to 150 ° C. Next, 0.04 g of stearic acid was charged into Labo Plastomill, and the modified conjugated diene polymer C and stearic acid were kneaded at 150 ° C. for 30 seconds, and then 0.4 g of water was charged and kneaded for another 30 seconds. Thus, a polymer composition was obtained.

[Comparative Example 4]
A polymer composition was obtained in the same manner as in Example 7, except that the resin temperature was changed to 30 ° C.

  Styrene unit content, vinyl bond content and Mw of modified conjugated diene-based polymer C in Examples 6 and 7, and Comparative Examples 3 and 4, content of organic acid based on 100 parts by mass of modified conjugated diene-based polymer C, polymer Table 3 shows the kneading conditions of the composition, ΔML, and the results of the cold flow test.

Example 8
(Modified conjugated diene polymer)
The inside of a 20 L stainless steel polymerization reactor equipped with a stirrer was purged with dry nitrogen. Next, 10.2 kg of industrial hexane, 600 g of 1,3-butadiene, 200 g of styrene, 6.07 mL of tetrahydrofuran, and 4.24 mL of ethylene glycol diethyl ether were charged into the polymerization reactor. Next, an n-hexane solution containing 12.98 mmol of n-BuLi was charged into the polymerization reactor, and the mixture was stirred at a stirring speed of 130 rpm and a temperature of 65 ° C in the polymerization reactor.

  While continuously supplying 900 g of 1,3-butadiene and 300 g of styrene to the above mixed solution, the mixed solution was further stirred for 2.5 hours under the above conditions to obtain a polymerization solution. Next, to the obtained polymerization solution, 12.98 mmol of [3- (diethylamino) propyl] trimethoxysilane was added, and the mixture was stirred for 15 minutes. Then, 20 mL of a hexane solution containing 0.79 mL of methanol was added, and the polymerization solution was further added. The mixture was stirred for 5 minutes to obtain a polymerization solution d1.

  8.0 g of "SUMILIZER GM" and 4.0 g of "SUMILIZER TP-D" were added to the polymerization solution d1, and a polymerization solution d2 containing the modified conjugated diene-based polymer D was obtained.

(Polymer composition)
To a polymerization solution d2 containing 600 g of the modified conjugated diene-based polymer D, 50 mL of a THF solution containing 1.2 g of stearic acid was added, stirred, and then spread on a vat. Next, the polymerization solution d2 spread in a vat was allowed to stand at room temperature for 12 hours, dried under reduced pressure at room temperature for 30.5 hours, and then heat-treated in a constant temperature bath set at 70 ° C. for 60 minutes to obtain a polymer composition. I got

[Comparative Example 5]
A polymer composition was obtained in the same manner as in Example 8, except that the temperature of the thermostat was changed to 50 ° C.

[Comparative Example 6]
A polymer composition was obtained in the same manner as in Example 8, except that the heat treatment time in the thermostat was changed to 30 minutes.

  Styrene unit content, vinyl bond content and Mw of modified conjugated diene-based polymer D in Example 8, Comparative Examples 5 and 6, content of organic acid based on 100 parts by mass of modified conjugated diene-based polymer D, polymer composition Table 4 shows the heat treatment conditions, ΔML, and cold flow test results.

Claims (6)

(1) a step of heat-treating a mixture of a modified conjugated diene-based polymer having a silicon atom in the structure and an organic acid at a temperature of 55 ° C. or more for 45 minutes or more, or (2) kneading at a temperature of 100 ° C. or more A method for producing an acid-modified conjugated diene-based polymer composition, comprising:
The method, wherein the change width of the Mooney viscosity at 100 ° C when the acid-modified conjugated diene-based polymer composition is stored at 50 ° C for 2 weeks is 10 or less.   The method according to claim 1, wherein the modified conjugated diene-based polymer has a group based on a compound having an alkoxysilyl group at a terminal.   The method according to claim 1, wherein the organic acid is an organic carboxylic acid. An acid-modified conjugated diene-based polymer having a silicon atom in the structure, and a compound derived from an organic acid,
An acid-modified conjugated diene-based polymer composition having a Mooney viscosity change at 100 ° C. of not more than 10 when stored at 50 ° C. for 2 weeks.   The polymer composition according to claim 4, wherein the content of the organic acid-derived compound is more than 0.2 parts by mass based on 100 parts by mass of the acid-modified conjugated diene-based polymer.   The polymer composition according to claim 4, wherein the organic acid is an organic carboxylic acid.