WO2008032417A1

WO2008032417A1 - Conjugated diene polymer, process for producing conjugated diene polymer, conjugated diene polymer composition and process for producing conjugated diene polymer composition

Info

Publication number: WO2008032417A1
Application number: PCT/JP2006/318797
Authority: WO
Inventors: Mayumi Oshima
Original assignee: Sumitomo Chemical Company, Limited
Priority date: 2006-09-15
Filing date: 2006-09-15
Publication date: 2008-03-20
Also published as: DE112006004023B4; DE112006004023T5; CN101511884A

Abstract

It is intended to provide a conjugated diene polymer, a process for producing the conjugated diene polymer, a conjugated diene polymer composition and a process for producing the conjugated diene polymer composition. The conjugated diene polymer is a conjugated diene polymer having a conjugated diene-based monomer unit and a group represented by the formula (I), wherein assuming the whole area of the molecular weight distribution curve obtained by gel permeation chromatography as 100%, the peak area of the molecular weight peak at the lowest molecular weight is 50% or more. [In the formula, R1 and R2 each independently represent a hydrocarbon group, a hydrocarbon oxy group or a hydroxyl group, m represents an integer of 0 to 10, and A1 represents a polar functional group free of an active hydrogen atom.]

Description

Description Conjugation-based polymer, method for producing conjugation-based polymer, conjugation-based polymer composition, and method for producing conjugation-based polymer composition

'

Technical field

The present invention relates to a conjugation-based polymer, a method for producing a conjugation-based polymer, a conjugation-based polymer composition, and a method for producing a conjugation-based polymer composition. Background art

In recent years, due to increasing interest in environmental issues, demand for fuel savings has been increasing for automobiles, and polymer compositions used for automobile tires are also required to have excellent fuel economy. ing. Examples of polymer compositions for automobile tires include polymer compositions containing a conjugate polymer such as polybutadiene or butadiene-styrene copolymer, and a filler such as carbon black. Is used. For example, a polymer composition using a polymer obtained by modifying a polymer obtained by copolymerizing butadiene and styrene using alkyllithium as a polymerization initiator with a tin halide compound as a conjugation-based polymer is known. (For example, JP-A-60-255838, USP4, 742, 124).

In addition, a polymer composition using a polymer obtained by copolymerizing butylene and styrene with alkyllithium as a polymerization initiator as a conjugated gen-based polymer and modified with acrylamide containing a dialkylamino group. (For example, Japanese Patent Laid-Open No. 11-21

7047, USP 5, 189, 109), a conjugated gen-based polymer, a polymer obtained by polymerizing butadiene or alkylating butadiene and styrene using alkyllithium as a polymerization initiator, Having alkoxysilane A polymer composition using a polymer modified with the above (for example, JP-A-63-186748, USP4, 957, 976, JP-A-2005-290355, US2 005/0203251 A1) It has been proposed as a polymer composition having good properties.

· Disclosure of invention

However, the polymer composition using the conventional conjugation-based polymer is not sufficiently satisfactory in terms of fuel saving when silica is used as the filler.

In such a situation, the problem to be solved by the present invention is that a conjugated gen-based polymer and a conjugated polymer that can obtain a polymer composition excellent in fuel efficiency when a filler is blended, particularly when silica is blended. The present invention provides a method for producing a gen-based polymer, a polymer composition obtained by blending a conjugated gen-based polymer and a silicic force, and a method for producing the polymer composition. .

As a result of intensive studies to solve the above problems, the present inventors have completed the present invention. '

That is, the present invention is a conjugated gen-based polymer having a monomer unit based on a conjugated gen and a group represented by the formula (I), wherein the total area of the molecular weight distribution curve obtained by gel permeation chromatography measurement is calculated. Provided is a conjugation polymer having a peak area of 50% or more of the molecular weight peak at the lowest molecular weight side at 100%.

[Wherein R ¹ and R ² are each independently a hydrocarbon group, a hydrocarbon oxy group or a hydroxyl group. M represents an integer of 0 to 10, and A ¹ represents a polar functional group having no active hydrogen. ]

The present invention provides a process for producing a conjugated gen-based polymer having steps 1 and 2. Step 1: In the presence of an alkali metal catalyst, in a hydrocarbon solvent, polymerize a monomer containing conjugation to obtain a conjugation-based polymer having an alkali metal derived from the catalyst at the end, and

Step 2: A key compound represented by the formula (IV) is added to a hydrocarbon solution of the conjugation polymer at a time to modify the conjugation polymer with the key compound.

[Wherein R ⁶ , R ⁷ and R ⁸ each independently represent a hydrocarbon group having 1 to 4 carbon atoms or a hydrocarbon oxy group having 1 to 4 carbon atoms, R ⁶ , R ⁷ And at least one of R ⁸ is a hydrocarbon oxy group having 1 to 4 carbon atoms, n represents an integer of 0 to 10 and A ² represents a polar functional group having no active hydrogen. The present invention also provides a conjugated diene polymer composition comprising the above conjugated diene polymer and silica. '

Furthermore, the present invention provides a process for producing a conjugated gen-based polymer composition having steps 1, 2, and 3.

Step 1: In the presence of an alkali metal catalyst, a monomer containing conjugation is polymerized in a hydrocarbon solvent to obtain a conjugation-based polymer having an alkali metal terminal from the catalyst.

Step 2: Add a gate compound represented by the formula (IV) to the hydrocarbon solution of the conjugated gen ¾ polymer at a time to modify the conjugated gen-based polymer with the key compound. as well as, Step 3: The conjugation polymer obtained in Step 2 and silica are blended.

R 6 '7—— Si —— (CH ₂ ) _n ~~ A ² (IV) R ⁸

[Wherein R ⁶ , R ⁷ and R ⁸ each independently represent a hydrocarbon group having 1 to 4 carbon atoms or a hydrocarbon oxy group having 1 to 4 carbon atoms, R ⁶ , R ⁷ And at least one of R ⁸ is a hydrocarbon oxy group having 1 to 4 carbon atoms, n represents an integer of 0 to 10 and A ² represents a polar functional group having no active hydrogen. ]

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 shows an example of a molecular weight distribution curve of a polymer.

Figure 2 shows an example of the boundary line between the lowest molecular weight peak and the adjacent peak. Figure 3 shows an example of the area of the molecular weight peak on the lowest molecular weight side.

BEST MODE FOR CARRYING OUT THE INVENTION The conjugation-based polymer of the present invention is a conjugation-based polymer having a monomer unit based on conjugation and a group represented by the formula (I), This is a polymer in which the peak area of the molecular weight peak on the lowest molecular weight side is 50% or more, assuming that the total area of the molecular weight distribution curve obtained by one chromatography chromatography is 100%.

[Wherein R ¹ and R ² each independently represents a hydrocarbon group, a hydrocarbon oxy group or a hydroxyl group, m represents an integer of 0 to 10 and A ¹ represents a polar functional group having no active hydrogen. Table group The Conjugation can include 1,3-butadiene, isoprene, 1,3-pentagene, 2,3-dimethyl_1,3-butadiene, 1,3-hexagen, etc. It may be a seed, or two or more. From the viewpoint of availability in production, 1,3-butadiene and isoprene are preferred.

R ¹ and R ² each independently represents a hydrocarbon group, a hydrocarbon oxy group or a hydroxyl group.

Examples of the hydrocarbon group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, and a t-butyl group. Further, the hydrocarbon group may be a group composed of a polymer chain such as a polymer chain having a monomer unit based on a conjugated diene. As these hydrocarbon groups, a methyl group and an ethyl group are preferable. '' Examples of the hydrocarbonoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group, and a t-butoxy group. As these hydrocarbonoxy groups, a methoxy group and a ethoxy group are preferable.

R ¹ and R ² are preferably a hydrocarbon oxy group, more preferably a methoxy group or an ethoxy group, from the viewpoint of improving fuel economy. m represents an integer of 0 to 10; From the viewpoint of improving fuel economy, it is preferably 3 or more, and from the viewpoint of improving economy during production, it is preferably 4 or less. A ¹ represents a polar functional group having no active hydrogen, a group represented by the formula (II), a formula (III ) And the like. ;

[Wherein, R ³ and R ⁴ each independently represent a hydrocarbon group having 1 to 6 carbon atoms which may have a nitrogen atom, an oxygen atom or a key atom, and R ³ and R ⁴ represent It may be bonded to form a ring structure. ]

[Wherein, X represents a divalent hydrocarbon group having 1 to 6 carbon atoms which may have an oxygen atom, and R ⁵ represents hydrogen or a hydrocarbon group having 1 to 6 carbon atoms. . ],

R ³ and R ⁴ each independently represent a hydrocarbon group having 1 to 6 carbon atoms which may have a nitrogen atom, an oxygen atom or a key atom.

Hydrocarbon groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, t-butyl, n-pentyl, neopentyl, isopentyl, and n- Xyl, cyclohexyl, phenyl, methoxymethyl, methoxyethyl, methoxypropyl, methoxybutyl, methoxypentyl, ethoxymethyl, ethoxyethyl, ethoxypropyl, ethoxybutyl, ethoxypentyl, trimethylsilyl Group, t-butyl dimethylsilyl group and the like.

R ³ and R ⁴ may be bonded, and examples of the group to which R ³ and R ⁴ are bonded include trimethylene group, tetramethylene group, pentamethylene group, and hexamethylene group. Xylene group such as xylene group, oxydipropylene group, etc .; group represented by one CH ₂ CH ₂ _NH—CH ₂ —, group represented by —CH ₂ CH ₂ —N═CH—, etc. And the like.

R ³ and R ⁴ are preferably a methyl group, an ethyl group, an n-propyl group, or a trimethylsilyl group. The group to which R ³ and R ⁴ are bonded is preferably a group represented by 1 CH ₂ CH ₂ —NH—CH ₂ —, a group represented by —CH ₂ CH ₂ —N═CH—. . ''.

X represents a divalent hydrocarbon group having 1 to 6 carbon atoms which may have an oxygen atom.

Examples of the hydrocarbon group include ethylene group, propylene group, butylene group, 1-oxyethylene group, 1-oxytrimethylene group, 1-oxytetramethylene group and the like.

X is preferably a 1-oxytrimethylene group. ,

R ⁵ represents hydrogen or a hydrocarbon group having 1 to 6 carbon atoms.

Hydrocarbon groups include methyl, ethyl, n-propyl, i'sopropyl, n-butyl, sec-butyl, t_butyl, n-pentyl, neopentyl, isopentyl, n —Hexyl group, cyclohexyl group, phenyl group and the like can be mentioned.

R ⁵ is preferably hydrogen or a methyl group. Examples of the group represented by the formula (II) include an acyclic amino group and a cyclic amino group.

Examples of acyclic amino groups include dimethylamino groups, jetylamino groups, and ethylmethyl. Ruamino group, di (methoxymethyl) amino group, di (methoxychetyl) amino group, di (ethoxymethyl) amino group, di (ethoxyethyl) amino group, di ((propyldimethylsilyl) amino) group, [di (Trimethylsilyl) amino group and the like can be mentioned.

Cyclic amino groups include: 1-pyrrolidinyl group, piperidino group, 1-hexamethyleneimino group, 1-heptamethyleneimino group, 1-octamethyleneimino group, 1-decamethyleneimino group, 1-dodecamethyleneimino group 1-polymethyleneimino group such as 1-tetradecamethylimino group and 1-year-old kutadecamethyleneimino group. Further, examples of the cyclic amino group include 1-imidazolyl group, 4,5-dihydro-1-1imidazolyl group, 1_imidazolidinyl group, 1-piperazinyl group, morpholino group and the like. Examples of the group represented by the formula (I I I) include a 3-glycidoxychetyl group and a 3-glycidoxypropyl group. ,

A ¹ is preferably a group represented by the formula (II) in view of economy and availability, and more preferably an acyclic amino group. The conjugation-based polymer of the present invention has monomer units based on other monomers in addition to monomer units based on conjugation (conjugation units) and groups represented by formula (I). You may do it.

Examples of other monomers include aromatic vinyl, vinyl nitrile, and unsaturated carboxylic acid ester.

As aromatic vinyl, styrene, α-methylstyrene, vinyl toluene, vinyl naphthalene, divinyl benzene, trivinyl benzene, divinyl naphthalene Can give.

Examples of vinyl nitrile include acrylonitrile. Examples of the unsaturated carboxylic acid ester include methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, and the like. Among these, styrene is preferable from the viewpoint of availability. The conjugation-based polymer of the present invention preferably has a monomer unit (aromatic vinyl unit) based on aromatic vinyl from the viewpoint of increasing strength, and the content of the aromatic vinyl unit is as follows. The total amount of conjugation units and aromatic vinyl units is 100% by weight, preferably 10% by weight or more (conjugation unit content is 90% by weight or less), more preferably 1%. 5% by weight or more (conjugation unit content is 85% by weight or less). Further, from the viewpoint of improving fuel efficiency, the content of the aromatic beer unit is preferably 50% by weight or less (conjugation unit content is 50% by weight or more), more preferably 45%. % By weight (conjugation unit content is 55% by volume or less). From the viewpoint of improving fuel economy, the conjugated gen-based polymer of the present invention is the conjugated gen-based polymer on the lowest molecular weight side, assuming that the total area of the molecular weight distribution curve obtained by gel permeation chromatography measurement is 100%. It is preferable that the molecular weight peak has a peak area of 50% or more. The peak area is

More preferably, it is 55% or more, more preferably 60% or more. Further, from the viewpoint of improving kneading processability, the peak area is preferably 95% or less, more preferably 90% or less. In the molecular weight distribution curve obtained by gel permeation chromatography, the molecular weight peak on the lowest molecular weight side is shown. Peak (hereinafter referred to as “peak L”) when the high molecular weight curve does not drop to the baseline (Figure 1), that is, when peak L overlaps with an adjacent peak. From the minimum point of the curve between the peak top of L and the peak top of the adjacent peak, a boundary line is set perpendicular to the baseline (Figure 2), and the low molecular weight region from the boundary line is the area of peak L (Fig. 3). The Mooney viscosity (ML _{1 + 4} ) of the conjugated gen-based polymer of the present invention is preferably 10 or more, more preferably 20 or more, from the viewpoint of increasing mechanical strength. Further, from the viewpoint of improving workability, it is preferably 200 or less, more preferably 'is 150 or less. The Mooney viscosity ML _{1 + 4} ) is measured at 100 ° C according to JIS K6300 (1994). The vinyl bond content of the conjugation-based polymer of the present invention is preferably 70 mol% or less, and more preferably from the viewpoint of improving fuel economy by setting the content of the conjugation unit to 1 G 0 mol%. 60 mol% or less. Further, from the viewpoint of improving the grip performance of the tire, it is preferably at least 10 mol%, more preferably at least 15 mol%. The amount of vinyl bonds is the absorption peak of the vinyl group by infrared spectroscopy.

It is obtained from the absorption intensity around 910 cn ¹ . · An example of the method for producing a conjugation-based polymer of the present invention is a method having the following steps 1 and 2.

Step 1: In the presence of an alkali metal catalyst, a monomer containing conjugation is polymerized in a hydrocarbon solvent to obtain a conjugation-based polymer having an alkali metal terminal of the catalyst.

Step 2: The cationization represented by the formula (IV) is added to the hydrocarbon solution of the conjugate polymer. Occasionally added, the conjugate polymer is modified with the key compound,

[Wherein R ⁶ , R ⁷ and R ⁸ each independently represent a hydrocarbon group having 1 to 4 carbon atoms or a hydrocarbon oxy group having 1 to 4 carbon atoms, R ⁶ , R ⁷ And at least one of R ⁸ is a hydrocarbon oxy group having 1 to 4 carbon atoms, n represents an integer of 0 to 10 and A ² represents a polar functional group having no active hydrogen. Examples of the alkali metal catalyst used in Step 1 include alkali metals, organic alkali metal compounds, complexes of alkali metals and polar compounds, and oligomers having alkali metals. '

Examples of the alkali metal include lithium, sodium, potassium, rubidium, and cesium. '' Organic alkali metal compounds include ethyl lithium, n-propyl lithium, iso-propyl lithium, n-butyl lithium, sec-butyl lithium, t-year-old cutyl lithium, n-decyl lithium, phenyl lithium, 2-naphthyl lithium 2-butyl-phenyllithium, 4-monophenyl-butyllithium, cyclohexyllithium, 4-cyclopentylpentyllithium, dimethylaminopropyllithium, jetylaminopropyllithium, t-butyldimethylsiloxypro Pyrlithium, N-morpholinopropyllithium, Lithium hexamethylene imide, Lithium pyrrolidide, Lithium piperidide, Lithium hepramethylene imide, Lithium dodecamethylene imide, 1,4-dilithiobutene-2, Sodium naphthalene, Sodium Biphenyl and lymnaphthalene can be listed. Examples of the complex of an alkali metal and a polar compound include a potassium-tetrahydrofuran complex and a potassium monoethoxyethane complex.

Examples of the oligomer having an alkali metal include 0: -methylstyrene tetramer sodium salt.

Among these, an organic lithium compound or an organic sodium compound is preferable, and an organic lithium compound or an organic sodium compound having 2 to 20 carbon atoms is more preferable. 'The hydrocarbon solvent used in step 1 is a solvent that does not deactivate the alkali metal catalyst, and examples thereof include aliphatic hydrocarbons, aromatic hydrocarbons, and alicyclic hydrocarbons.

Aliphatic hydrocarbons include propane, n-butane, iso-butane, n-pentane, iso-pentane, n-hexane, propene, 1-butene, iso-butene, trans-2-butene, cis-one 2-butene, 1-pentene, 2-pentene, 1-hexene, 2-hexene and the like.

Examples of aromatic hydrocarbons include benzene, toluene, xylene, and ethylbenzene.

Examples of alicyclic hydrocarbons include cyclopentane and cyclohexane.

'These can be used alone or in combination of two or more. Among these, hydrocarbons having 2 to 12 carbon atoms are preferable. In Step 1, a monomer containing a conjugated gen is polymerized to produce a conjugated gen-based polymer having an alkali metal derived from the above-mentioned alkali metal catalyst at its terminal.

Conjugation generators include 1,3-butadiene, isoprene, and 1,3-pen evening. 2,3-dimethyl-1,3-butadiene, 1,3-hexagen, and these may be used alone or in combination of two or more. Of these, 1,3-butadiene and isoprene are preferred from the viewpoint of availability.

In step 1, polymerization may be carried out with the conjugate conjugate alone, or polymerization may be carried out by combining the conjugate conjugate with another monomer.

Other monomers include aromatic vinyl, vinyl nitrile, unsaturated carboxylic acid ester and the like. -Examples of aromatic pinyl include styrene, α-methylstyrene, vinyl toluene, vinyl naphthalene, divinyl benzene, trivinyl benzene, and divinyl naphthalene. '

Examples of benzonitrile include acrylonitrile. Examples of the unsaturated carboxylic acid ester include methyl acrylate, ethyl acrylate, methyl methacrylate, and ethyl methacrylate. Among these, styrene is preferable from the viewpoint of availability. '

, Polymerization in step 1 is an agent that adjusts the vinyl bond content of the conjugation unit. Conjugation system The distribution of monomer units based on conjugation units and monomers other than conjugation units in the polymer chain is adjusted. Do this in the presence of agents (hereinafter collectively referred to as “regulators”).

Examples of the adjusting agent include ether compounds, tertiary amines, and phosphine compounds.

Examples of ether compounds include tetrahydrofuran, tetrahydropyran, and 1,4-dioxane, cyclic ethers; aliphatic monoethers such as jetyl ether and dibutyl ether; ethylene glycol dimethyl ether, ethylene glycol jetyl ether, and ethylene glycol. Dibutyl ether, diethylene glycol Examples include aliphatic ethers such as rugetyl ether and diethylene glycol dibutyl ether; aromatic ethers such as diphenyl ether and anisole.

Tertiary amines include triethylamine, tripropylamine, tributylamine, N, N, N ', N'-tetramethylethylenediamine, N, N-jetylaniline, pyridine, quinoline, etc. it can.

Examples of the phosphine compound include trimethylphosphine, triethylphosphine, and triphenylphosphine.

These may be used alone or in combination of two or more. The polymerization temperature in step 1 is usually from 30 to 100 ° C., preferably from 35 to 65, and the polymerization time is usually from 10 minutes to 5 hours. In step 2, the carbonyl compound polymer represented by formula (IV) is added to the hydrocarbon solution of the conjugated gen polymer having the alkali metal terminal obtained in step 1, and the conjugated gen polymer is gained. Denature with elemental compounds.

'[Wherein R ⁶ , R ⁷ and R ⁸ each independently represents a hydrocarbon group having 1 to 4 carbon atoms or a hydrocarbon oxy group having 1 to 4 carbon atoms, R ⁶ , R ⁷ and at least R ⁸

One is a hydrocarbon oxy group having 1 to 4 carbon atoms, n represents an integer of 0 to 10, and A ² represents a polar functional group having no active hydrogen. ]

R ⁶ , R ⁷ and R ⁸ each independently represent a hydrocarbon group having 1 to 4 carbon atoms or a hydrocarbon oxy group having 1 to 4 carbon atoms. At least one of R ⁶ , R ⁷ and R ⁸ is charcoal It is preferably a hydrocarbon oxy group having 1 to 4 elemental atoms, and R ⁶ , R ⁷ and R ⁸ are all hydrocarbon oxy groups having 1 to 4 carbon atoms.

The hydrocarbon groups having 1 to 4 carbon atoms of R ⁶ , R ⁷ and R ⁸ include methyl group, ethyl group, η-propyl group, isopropyl group, η-butyl group, sec-butyl group, t One butyl group can be mentioned. As these hydrocarbon groups, a methyl group or an ethyl group is preferable.

Further, as the hydrocarbonoxy group having 1 to 4 carbon atoms of RR ² and R ^3, a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group , T-butoxy group. These hydrocarbon hydrocarbon oxy groups are preferably methoxy groups or ethoxy groups.

n represents an integer of 0 to 10; From the viewpoint of improving fuel economy, it is preferably 3 or more, and from the viewpoint of improving economy during production, it is preferably 4 or less.

A ² represents a polar functional group having no active hydrogen, and examples thereof include a group represented by formula (II) and a group represented by 'formula' (III). ,

R [In the formula, X represents a divalent hydrocarbon group having 1 to 6 carbon atoms which may have an oxygen atom, and R ⁵ represents hydrogen or a hydrocarbon group having 1 to 6 carbon atoms. . ]

In A ² , examples of the group represented by formula (II), the group represented by formula (III), R ³ , R ⁴ , R ^{5. And} X are each represented by formula (II) in A ¹ a group represented by the group represented by formula (III), are the same as exemplified for R ^3, RR ⁵ and X, a group represented by the formula ([pi), a group represented by the formula (III), R ³ , R ⁴ , R ′ ⁵ and X are preferably groups represented by the formula (II) in A ¹ , a group represented by the formula (III), R ³ , R ⁴ , R ⁵ and The same as the preferable group of X. The preferred group for A ² is the same as the preferred group for A ¹ . As the compound represented by the formula (IV), as the compound in which A ² is an acyclic amino group represented by the formula (II), [3- (dimethylamino) propyl] trimethoxysilane, [3- ( Jetylamino) propyl] trimethoxysilane, [3- (dimethylamino) propyl] triethoxysilane, [3- (jetylamino) pro'pyl] triethoxysilane, [(3-methyl-3-ethylamino) propyl] trimethoxysilane, [(3-Methyl_3-Ethylamino) propyl] triethoxysilane, [3- (Dimethylamino) propyl] methyldimethoxysilane, [3- (Jetylamino) propyl] methyldimethoxysilane, [3- (Dimethylamino) propyl] ethyl dimethoxy Silane, [3- (Jetylamino) propyl] ethyldimethoxysilane, [3- (Dimethylamino) propyl] Dimethylmethoxysilane, [3- (dimethylamino) propyl] jetylmethoxysilane, [3- (Jetylamino) propyl] dimethylmethoxysilane, [3- (Jetylamino) propyl] jetylmethoxysilane, [(3-Methyl. 3-Ethylamino) propyl] methyldimethoxysilane, [(3-Methyl-3-ethylamino) propyl] ethyldimethoxysilane, [3 (dimethylamino) propyl] methyljetoxysilane, [3- (Jetylamino) B) Propyl] methyljetoxysilane, [3- (dimethylamino) propyl] ethyljetoxysilane, [3- (Jetylamino) propyl] ethyljetoxysilane, [3- (dimethylamino) propyl] dimethylethoxy Silane, [3- (dimethylamino) propyl] jetylethoxysilane, [3- (Dethylamino) propyl] dimethylethoxysilane, [3- (Jetylamino) propyl] jetyloxysilane, [(3-methyl-3-ethylamino) propyl ] Methyl jetoxy silane, [(3-Methyl-3-ethylamino) propyl] ediljetoxysilane, [3- (Dimethoxymethylamino) propyl] trimethoxysilane, [3- (Dimethoxetylamino) propyl] trimethoxysilane, [ 3- (Dimethoxymethylamino) propyl] triethoxy Silane, [3- (dimethoxyethylamino) propyl] triethoxysilane, [3- (diethoxyethylamino) propyl] trimethoxysilane, [3- (diethoxymethylamino) propyl] trimethoxysilane [3- (diethoxyethylamino) propyl] 'triethoxysilane, [3- (Jetoxymethylamino) propyl] triethoxysilane, {3- [di (卜 -methylsilyl) amino] propyl} プロピル -trimethoxysilane, {3 -— [Di (trimethylsilyl) amino] propyl} triethoxysilane, {3- [di (t-butylmethylsilyl) amino] propyl} trimethoxysilane, {3- [di (t_ptyldimethylsilyl) amino ] Propyl} triethoxysilane, {3- [di (trimethylsilyl) amino] propyl} methyldimethoxysilane, {3- [di (trimethylsilyl) [Amino] propyl} methyl methoxysilane, {3- (di (t-butyldimethylsilyl) amino] propyl} methyldimethoxysilane, {3- (di (t-butyldimethylsilyl)

) Amino] propyl} methyljetoxysilane, {3- [di (trimethylsilyl) amino] propyl} dimethyl silane, {3- [di (trimethylsilyl) amino] propyl} dimethylethoxysilane, {3- [di ( t-Butyldimethylsilyl) amino] propyl} dimethylmethoxysilane, {3— [di (t-butyldimethyl) Rusilyl) amino] propyl}, [3- (ethylmethylamino) propyl] trimethyoxysilane, [3- (ethylmethylamino) propyl] triethoxysilane, [3- (ethylmethylamino) propyl] Methyldimethoxysilane, [3- (ethylmethylamino) propyl] ethyldimethoxysilane, [3- (ethylmethylamino) propyl] methyljetoxysilane, [3- (ethylmethylamino) propyl] ethyl Jetoxysilane and the like can be mentioned.

From the viewpoint of improving fuel economy, the key compounds in which A ² is an acyclic amino group represented by the formula (II) are [3- (Jetylamino) propyl] trimethoxysilane, [3- (dimethylamino) propyl. Triethoxysilane is preferred. Among these, [3-(jetylamino) propyl] methyldimethoxysilane is preferable from the viewpoint of achieving both the fuel saving cost and the availability of the compound and the long-term storage stability.

Examples of the silicon compound represented by the formula (IV) include 3-morpholinopropyltrimethoxysilane, 3-morpholinopropyltriethoxysilane, and the like, wherein A ² is a cyclic amino group represented by the formula (II). , 3-morpholinopropylmethyldimethyl dioxy

Ethoxysilane, 3-piperidinopropylmethyldimethoxysilane, 3-piperidinopropylethyldimethoxysilane, 3-piperidinopropylmethyljetoxysilane, 3-piperidinopropylethylmethoxysilane, N_ (3— Trimethyoxysilylpropyl) —4,5-dihydroimidazole, N- (3-triethoxysilylpropyl) —4,5-dihydroimidazole, N- (3-trimethoxysilylpropyl pill) -4,5-imidozo N, (3-triethoxysilylpropyl) -4,

5-imidazole, 3-hexamethyleneiminopropyltrimethoxysilane, 3-hexamethyleneiminopropyltriethoxysilane, 3-hexamethyleneimi Nopropylmethyldimethoxysilane, 3-hexamethyleneiminopropylethyl dimethoxysilane, 3-hexamethyleneiminopropylmethyljetoxysilane.

From the standpoint of improving fuel economy, N- (3-trimethoxysilylpropyl) —4,5-dihydroimidazole, N is a key compound in which A ² is a cyclic amino group represented by the formula (II). -(3-triethoxysilylpropyl) —4,5-dihydroimidazole, N- (3-trimethoxysilylpropyl) _ 4,5-imidazole, N- (3-triethoxysilylpropyl) -4,5 —Imidazole is preferred.

Examples of the key compound represented by the formula (IV) include 3-glycidoxypropyl trimethoxysilane, 3-glycidoxy as a key compound in which A ² is a group represented by the formula (III). Examples thereof include propyltriethoxysilane, 3-dalysidoxypropylmethyldimethoxysilane, 3-glycidoxypropylethyldimethoxysilane, and 3-glycitoxysilane. 'The key compound in which A ² is a group represented by the formula (III) is as follows: From the viewpoint of improving the fuel efficiency, the availability of the compound, and the long-term storage stability, (Doxypropyl) Trimethoxysilane is preferred.

The addition of the silicon compound represented by formula (IV) in Step 2 is performed at a time while the hydrocarbon solution is stirred. The addition rate of the key compound is preferably 6 mmol Zsec per unit volume and unit time of the hydrocarbon solvent from the viewpoint of improving fuel economy (from the viewpoint of increasing the peak L area of the conjugated gen-based polymer). Zm ³ or more, more preferably 10 mmol / sec Zm ³ or more. In addition, from the viewpoint of improving operability, the supplementary acceleration is preferably 100 million mmol / sec or less Zm ³ .

The addition amount of the silicon compound is the same as that of the alkali metal catalyst used in step 1. From the viewpoint of improving fuel economy per mole (from the viewpoint of increasing the peak L area of the conjugated gen-based polymer), it is preferably at least 0.5 mole, more preferably at least 0.8 mole. In addition, from the viewpoint of improving economics during production, the amount is preferably 10 mol or less, more preferably 2 mol or less.

The silicon compound may be added to the hydrocarbon solution as a solution in a solvent that does not deactivate the alkali metal catalyst such as tetrahydrofuran or hexane. The concentration of the conjugated gen-based polymer in the hydrocarbon solution before adding the silicon compound is from the viewpoint of improving fuel efficiency (from the viewpoint of increasing the peak L area of the conjugated gen-based polymer). It is preferably 30% by weight or less, more preferably 20% by weight or less. From the viewpoint of increasing productivity, it is preferably 5% by weight or more, and more preferably 10% by weight or more.

From the viewpoint of improving fuel economy (in terms of increasing the peak L area of the conjugate polymer), the stirring speed of the hydrocarbon solution when adding the silicon compound is preferably 30 rpm or more, more preferably 50 rpm or more, and even more preferably 7 O rpm. Further, from the viewpoint of improving economy, it is preferably 40 O r pm or less, more preferably 3 0 0 r pm, and further preferably 2 0 0 r pm or less. Further, the temperature of the hydrocarbon solution when adding the silicon compound is usually 35 to 65 T :.

It is preferable to stir the hydrocarbon solution after adding the silicon compound. The stirring speed is usually 100 rpm or more, the temperature is usually 35 or more, and the time is usually 1 second to 30 minutes. In addition, before or after the addition of the silicon compound represented by the formula (IV), the hydrocarbon solution of the conjugated diene polymer having an alkali metal terminal obtained in step 1 is added to the following formula: The indicated coupling agent may be added.

(Wherein R ⁹ represents an alkyl group, an alkenyl group, a cycloalkenyl group or an aromatic hydrocarbon group, M represents a silicon atom or a tin atom, L represents a halogen atom, a is an integer of 0 to 2) Represents)

Examples of the coupling agent represented by the above formula include silicon tetrachloride, methyl trichloro.rosilan, dimethyldichlorosilane, trimethylchlorosilane, tin tetrachloride, methyl trichlorotin, dimethyldichlorotin, trimethylchlorotin, and the like. .

The addition amount of the coupling agent is preferably 0.03 mol or more, more preferably 0.0 mol or more, from the viewpoint of improving the kneading processability of the conjugate polymer based on 1 mol of the alkali metal of the alkali metal catalyst. 5 moles or more. Further, from the viewpoint of improving fuel economy, it is preferably 0.4 mol or less, more preferably 0.3 mol or less. ''

, Conjugated polymers can be obtained by a known recovery method, for example, (1) a method of adding a coagulant to a hydrocarbon solution of a conjugated diene polymer, (2) By the method of adding a team, it can be recovered from the hydrocarbon solution of the conjugate conjugate polymer after the treatment in Step 2. The recovered conjugation polymer may be dried with a known dryer such as a band dryer or an extrusion dryer. The conjugated gen-based polymer of the present invention can be used as a conjugated gen-based polymer composition by blending other polymer components and additives.

Examples of other polymer components include conventional styrene-butadiene copolymer rubber, polybutadiene rubber, butadiene-isoprene copolymer rubber, and butyl rubber. be able to. In addition, natural rubber, ethylene-propylene copolymer, ethylene-octene copolymer and the like can also be mentioned. Two or more of these polymer components may be used in combination.

Known additives can be used, such as sulfur vulcanizing agents; vulcanization accelerators such as thiazol vulcanization accelerators, thiuram vulcanization accelerators, and sulfenamide vulcanization accelerators. Vulcanization activators such as stearic acid and zinc oxide; organic peroxides; fillers such as silica, carbon black, calcium carbonate and talc; silane coupling agents; extension oils; processing aids; Agents: Lubricants can be exemplified. In the case of using a conjugation-based polymer composition in which a filler is blended with the conjugation-based polymer of the present invention, it is preferable to use silica as the filler.

As a method for producing a conjugation polymer composition by blending other polymer components or additives into the conjugation polymer of the present invention, known methods, for example, using each component as a mouthpiece A kneading method using a known mixer such as Banbury can be used.

In the case of a conjugated gen-based polymer composition in which silica is added to the conjugated gen-based polymer of the present invention, the amount of silica is usually 10 to 150 parts by weight. In addition, the blending amount is preferably 20 parts by weight or more, more preferably 30 parts by weight, from the viewpoint of improving fuel efficiency, with the blending amount of the conjugate conjugate polymer of the present invention being 100 parts by weight. Or more. Further, from the viewpoint of enhancing the reinforcing property, it is preferably 120 parts by weight or less, more preferably 100 parts by weight or less.

In the case where other polymer components are blended with the conjugate conjugate polymer of the present invention, the blending amount of the conjugate polymer of the present invention is 10% from the viewpoint of improving fuel economy. As 0 part by weight, it is preferably 10 parts by weight or more, more preferably 20 parts by weight or more.

When a filler other than silica is blended in the conjugated gen-based polymer of the present invention, The blending amount of the other filler is preferably 50 parts by weight or less, more preferably 30 parts by weight, from the viewpoint of improving fuel economy, with the total blending amount of the filler being 100 parts by weight. It is as follows. In addition, from the viewpoint of enhancing reinforcement, the amount is preferably 1 part by weight or more, more preferably 3 parts by weight or more. An example of a method for producing a composition comprising the conjugation polymer of the present invention and silica is a production method having the following step 3 in addition to the above step 1 and step 2.

Step 3: The conjugation polymer obtained in Step 2 and silica are blended. 'In step 3, other polymer components and other additives may be blended. As a blending method in Step 3, a known method, for example, a method of kneading each component with a known mixer such as a roll or a Banbury machine can be used.

As the kneading conditions of Step 3, when additives other than the vulcanizing agent and the vulcanization accelerator are blended, the kneading temperature is usually 50 to 200 ° C., preferably 80 to 19. The kneading time is usually 30 seconds to 30 minutes, preferably 1 minute to 30 minutes. When a vulcanizing agent and a vulcanization accelerator are blended, the kneading temperature is usually 100 ° C. or lower, preferably room temperature to 80 ° C. A composition containing a vulcanizing agent and a vulcanization accelerator is usually used after vulcanization treatment such as press vulcanization. The vulcanization temperature is usually

1 2 0 to 2 0 0, preferably 1 4 0 to 1 8 0.

In step 3, the compounding amount of the conjugation polymer obtained in step 2, the compounding amount of silica, the compounding amount of the other polymer components, and the compounding amount of the filler other than silica are as described above. An amount is preferred. The conjugate conjugate polymer and conjugate conjugate polymer composition of the present invention are excellent in fuel efficiency. It also has good processability, grip, wear resistance, and strength. The conjugation-based polymer and the conjugation-based polymer composition of the present invention are used for tires, shoe sole flooring materials, vibration-proofing materials and the like, and are particularly preferably used for tires. Example

Hereinafter, the present invention will be described by way of examples.

The physical properties were measured by the following method.

1. Mooney viscosity (ML _{1 + 4} ) '-Measured at 100 ° C according to JIS K6300 (1994). 2. Vinyl content (Unit: mol%)

It was determined from the absorption intensity around 910 cm- ^1, which is the vinyl group absorption peak, by infrared spectroscopy.

3. Content of styrene unit (unit:% by weight) '' Calculated from refractive index according to JIS · K6383 (1995). ,

4. Molecular weight distribution curve

The measurement was performed under the following conditions (1) to (8) using a gel permeation chromatograph (GPC) method.

(1) Equipment: Tosoh HLC-8020

(2) Separation column: Tosoh GMH-XL (two in series)

(3) Measurement temperature: 40

(4) Carrier: Tetra.hydrofuran

(5) Flow rate: 0.6mLZ min

(6) Injection volume: 5 ^ L (7) Detector: Differential refraction

(8) Molecular weight standard: Standard polystyrene

5. Fuel saving

Using a viscosity measuring device (manufactured by Toyo Seiki Co., Ltd.), loss tangent (t an <5 (70)) at a temperature of 70 ° C was measured under the conditions of 1% strain and 10 Hz frequency. The smaller this value, the better the fuel economy. Example 1

A stainless steel polymerization reactor with an internal volume of 20 liters was washed, dried, and replaced with dry nitrogen. Hexane (specific gravity 68gZcm ³ ) 10.2kg, 1,3-butadiene 608g, styrene 192g, tetrahydrofuran 6 lml, ethylene glycol jetyl ether 5.0ml was added. Next, n-butyl lithium 13.8 mmo 1 was added as an n-hexane solution, the temperature in the polymerization reactor was adjusted to 65, and 1,3-butadiene and styrene were fed to the polymerization reactor. Polymerization was performed for 3 hours to obtain a polymer solution. In the 3-hour polymerization, 1,3-butadiene was supplied in 912 g, and styrene was supplied in 288 g. The obtained polymer solution was stirred at a stirring speed of 130 rpm, and [3- (Jetylamino) propyl] trimethoxysilane 11.3 mm o 1 was added to the polymer solution in 1 second. Was stirred for 60 minutes, 10 ml of methanol was then added to the polymer solution, and the polymer solution was further stirred for 5 minutes. 2—Evening Shaributyl— 6— (3-Evening Shary Butyl 2-hydroxy-5-methylbenzyl) —4 Monomethylphenylacrylate (Sumitomo Chemical) Made by Gaku, Trade name: Sumilizer GM.) 8 g, Penyu erythrityl tetrakis (3- Laurylpropionate) (Sumitomo Chemical, each product: Sumilizer TP-D) 4 g, then heavy The combined solution was evaporated at room temperature for 24 hours, and further dried under reduced pressure at 55 ° C. for 12 hours to obtain a polymer. Table 1 shows the measurement results of the physical properties of the polymer. 100 parts by weight of the obtained polymer, silica (made by Degussa, trade name: Ultrasil VN3-G) 78.4 parts by weight, silane coupling agent (made by Degussa, trade name: Si 69) 6.4 weight , Rikiichibon 6.4 parts by weight, extension oil (manufactured by Kyodo Oil Co., Ltd., trade name: X-140) 47. 6 parts by weight, anti-aging agent (manufactured by Sumitomo Chemical, trade name: Antigen 3C) 1. 5 parts by weight, stearic acid 2 parts by weight, zinc white 2 parts by weight, vulcanization accelerator (manufactured by Sumitomo Chemical Co., Ltd., trade name: Soxinol CZ) 1 part by weight, vulcanization accelerator (manufactured by Sumitomo Chemical Co., Ltd., trade name: Soxinol) D) 1 part by weight, wax (manufactured by Ouchi Shinsei Chemical Co., Ltd., product name: Sannok N) 1.5 parts by weight, 1.4 parts by weight of sulfur were kneaded in a lab plast mill, and the resulting kneaded product was Molded into a sheet with a 6-inch roll. : Sheets were heated at 160 ° C for 45 minutes to vulcanize, and the fuel efficiency of the vulcanized sheets was evaluated. Table 1 shows the evaluation results. Comparative Example 1

n-Butyllithium 20. 7 mmo 1 was added as an n-hexane solution to initiate polymerization, and [3- (Jetylamino) propyl] trimethoxysilane 18.2 mm o 1 was added to 50 ml of hexane. The same procedure as in Example 1 was performed except that the solution was added to the polymer solution over 10 minutes. Table 1 shows the results of measuring the physical properties of the polymer and the fuel efficiency evaluation results of the vulcanized sheet. table 1

Example 2

A stainless steel polymerization reactor with an internal volume of 20 liters was washed, dried and replaced with dry nitrogen, then hexane (specific gravity 68 g // cm ³ ) 10.2 kg, 1,3-butagen 608 g, styrene 192 g, tetrahydrofuran (6 lml), and ethylenedalchol jetyl ether (5.0 ml) were added. Next, n-butyllithium 16.7 mmo 1 was added as an n-hexane solution, the temperature in the polymerization reactor was adjusted to 65, and 1,3-butadiene and styrene were fed to the polymerization reactor. Polymerization was performed for 3 hours to obtain a polymer solution. In the 3-hour polymerization, 1,3-butadiene was supplied in 912 g, and styrene was supplied in 288 g. The resulting polymer solution was stirred at a stirring speed of 130 rpm, and 3-glycidoxyl pyrtrimethoxysilane 14.3 mm o 1 was added to the polymer solution in 1 second, and the polymer solution was stirred for 60 minutes. Next, 10 ml of methanol was added to the polymer solution, and the polymer solution was further stirred for 5 minutes. · '2-Tertiary butyl-6-(3-evening butyl-2-hydroxy-5-methyl benzyl) — 4-methyl phenyl acrylate (manufactured by Sumitomo Chemical Co., Ltd., trade name: Sumilyzer 1) GM) 8 g, Penyu erythrityltetrakis (3-laurylpropionate) (manufactured by Sumitomo Chemical Co., Ltd., trade name: Sumilizer TP-D) 4 g ¾ Evaporated and further dried under reduced pressure at 55 ° C for 12 hours to obtain a polymer. Table 2 shows the measurement results of the physical properties of the polymer. 10 parts by weight of the obtained polymer, silica (manufactured by Degussa, trade name: Ultrasil)

VN3-G) 78. 4 parts by weight, silane coupling agent (Degussa, product name: Si 69) 6.4 parts by weight, carbon 6.4 parts by weight, extension oil (manufactured by Kyodo Oil Co., Ltd., product) Name: X—140) 47. 6 parts by weight, anti-aging agent (trade name: Antigen 3C, manufactured by Sumitomo Chemical Co., Ltd.) 1.5 parts by weight, stearic acid 2 parts by weight, zinc white 2 parts by weight, vulcanization accelerator

(Sumitomo Chemical Co., Ltd., trade name: Soxinol CZ) 1 part by weight, Vulcanization accelerator (Sumitomo Chemical Co., Ltd., trade name: Soxinol D) 1 part by weight, wax (Ouchi Shinsei Chemical Co., Ltd., trade name: Sunnock) N) 1.5 parts by weight and 1.4 parts by weight of sulfur were kneaded with a lab plast mill, and the resulting kneaded material was formed into a sheet with a 6-inch mouthpiece. Sheet

Vulcanization was performed by heating at 160 ° C for 45 minutes, and the fuel efficiency of the vulcanized sheet was evaluated. Table 2 shows the evaluation results. Comparative Example 2.

The same procedure as in Example 2 was conducted, except that 3-glycidoxypropyltrimethoxysilane was added to the polymer solution as a 50 ml tetrahydrofuran solution over 10 minutes. Table 2 shows the physical property measurement results of the obtained polymer and the fuel efficiency evaluation results of the vulcanized sheet. ,

Table 2

Industrial applicability

According to the present invention, when a filler is blended, particularly when silica is blended, a conjugation-based polymer capable of obtaining a polymer composition excellent in fuel-saving properties, a method for producing a conjugated-gen polymer, There are provided a polymer composition comprising a polymer based on silica and a method for producing the polymer composition.

Claims

Claims Conjugated gen-based polymer having monomer units based on conjugation and a group represented by the following formula (I), wherein the molecular weight distribution curve obtained by gel permeation chromatography measurement A conjugated gen-based polymer in which the total area is 100% and the peak area of the lowest molecular weight peak is 50% or less.

[In the formula, R ¹ and R ² each independently represent a hydrocarbon group, a hydrocarbon oxy group or a hydroxyl group, m represents a number from 0 to 10, and A ¹ represents a polar functional group having no active hydrogen. 'Represents a group. ]

The conjugate polymer according to claim 1, wherein A ^{1 in the} formula (I) is a group represented by the following formula (II) or (III).

[Wherein R ³ and R ⁴ each independently represents a hydrocarbon group having 1 to 6 carbon atoms which may have a nitrogen atom, an oxygen atom or a key atom, and R ³ and R ⁴ represent It may combine to form a ring structure. ] (III)

[In the formula, X represents a divalent hydrocarbon group having 1 to 6 carbon atoms which may have an oxygen atom, and R ⁵ represents hydrogen or a hydrocarbon group having 1 to 6 carbon atoms. . ]

3. The syngeneic gen-based polymer according to claim 1 or 2, wherein R ¹ and R ^{2 in} the formula (I) are hydrocarbonoxy groups.

4. A process for producing a conjugated gen-based polymer having steps 1 and 2.

Step 1: In the presence of an alkali metal catalyst, in a hydrocarbon solvent, polymerize a monomer containing conjugation to obtain a conjugation-based polymer having an alkali metal derived from the catalyst at its terminal, and

Step 2: Temporarily adding the cage compound represented by the following formula (IV) to the hydrocarbon solution of the conjugate conjugated polymer to modify the conjugate conjugate polymer with the conjugated compound. . -

[Wherein R ⁶ , R ⁷ and R ⁸ each independently represents a hydrocarbon group having 1 to 4 carbon atoms or a hydrocarbon oxy group having 1 to 4 carbon atoms, R ⁶ , R ⁷ And at least one of R ⁸ is a hydrocarbon oxy group having 1 to 4 carbon atoms, n represents an integer of 0 to 10 and A ² represents a polar functional group having no active hydrogen. ]

5. In step 2, the addition amount of the silicon compound represented by formula (IV) is 0.1 to 10 moles per mole of alkali metal of the alkali metal catalyst used in step 1, and the formula (IV) 2. The method according to claim 1, wherein the addition rate of the silicon compound represented by the formula (1) is 6 mmol Zsec Zm ³ or more per unit volume and unit time of the hydrocarbon solution.

6. The method according to claim 4 or 5, wherein A ^{2 in the} formula (IV) is a group represented by the following formula (II) or (III).

[In the formula, R ³ and R ⁴ each independently represent a hydrocarbon group having 1 to 6 carbon atoms which may have a nitrogen atom, an oxygen atom or a silicon atom, and R ³ and R ⁴ represent It may combine to form a ring structure. ] (III)

[Wherein X may have an oxygen atom, and may represent a divalent hydrocarbon group having 1 to 6 carbon atoms, R ⁵ represents hydrogen or a hydrocarbon group having 1 to 6 carbon atoms. To express. The method according to claim 4, wherein all of ⁶ , R ⁷ and R ^{8 in} (IV) are hydrocarbon oxy groups having 1 to 4 carbon atoms. 'Conjugated polymer obtained by the production method according to any one of claims 4 to 7. .

A conjugation-based polymer composition comprising the conjugation-based polymer according to any one of claims 1 to 3 and a silicic force. '

The conjugate polymer composition according to claim 9, wherein the compounding amount of silica is 10 to 150 parts by weight per 100 parts by weight of the conjugate polymer.

A process for producing a conjugated gen-based polymer composition comprising steps 1, 2 and 3.

Step 1: In the presence of an alkali metal catalyst, in a hydrocarbon solvent, a monomer containing a conjugation monomer is polymerized to obtain a conjugation-based polymer having an alkali metal derived from the catalyst at the end.

Step 2: To the hydrocarbon solution of the conjugation-based polymer, a keen compound represented by the following formula (IV) is added at a time, and the conjugation-based polymer is changed with the cathene compound. Have sex and

Step 3: The conjugation polymer obtained in Step 2 and silica are blended.

[Wherein R ⁶ , R ⁷ and R ⁸ each independently represent a hydrocarbon group having 1 to 4 carbon atoms or a hydrocarbon oxy group having 1 to 4 carbon atoms, R ⁶ , R ^At least one of ⁷ and R ⁸ is a hydrocarbon oxy group having 1 to 4 carbon atoms, n represents an integer of 0 to 10 and A ² represents a polar functional group having no active hydrogen. ]

2. In step 2, the addition amount of the silicon compound represented by formula (IV) is 0.1 to 10 moles per mole of alkali metal of the alkali metal catalyst used in step 1, and the formula (IV 2. The method according to claim 11, wherein the addition rate of the silicon compound represented by formula (1) is at least 6 mmol Zsec Zm ³ per unit volume and unit time of the hydrocarbon solution. ,,

3. The method according to claim 11 or 12, wherein A ^{2 in the} formula (IV) is a group represented by the following formula (II) or (III).

R ³

~ "Ku (I I)

[Wherein R ³ and R ⁴ each independently represents a hydrocarbon group having 1 to 6 carbon atoms which may have a nitrogen atom, an oxygen atom or a key atom, and R ³ and R ⁴ represent It may combine to form a ring structure. ] [In the formula, X represents a divalent hydrocarbon group having 1 to 6 carbon atoms which may have an oxygen atom; R ⁵ represents hydrogen or a hydrocarbon group having 1 to 6 carbon atoms; To express. 14. The method according to any one of claims 11 to 13, wherein R ⁶ , R ⁷ and R ^{8 in the} formula (IV) are all hydrocarbon oxy groups having 1 to 4 carbon atoms.

15. The method according to any one of claims 11 to 14, wherein in step 3, 10 to 150 parts by weight of silica is blended per 100 parts by weight of the conjugation polymer obtained in step 2.