JP2002284814A - Production method for modified conjugated diene polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for stably producing a modified conjugated diene polymer with a high degree of modification by using a specific modifier. SOLUTION: In a method for producing a modified conjugated diene polymer by polymerizing a monomer component comprising a conjugated diene monomer alone or together with an aromatic vinyl monomer in a hydrocarbon solvent in the presence of an organolithium compound as an initiator and reacting the resultant conjugated diene polymer with a compound having a group reactive with the active terminals of the polymer, (1) the monomer component contains less than 200 ppm impurities comprising acetylene compounds and allene compounds, (2) the monomer component alone or together with a hydrocarbon solvent is treated with an organometallic compound and then the monomer component is fed to a polymerizer; and (3) after the polymerization, a modifier is added to form a modified component in a content of 60 wt.% or higher.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a process for producing a modified conjugated diene-based polymer using a specific modifying agent, whereby a modified conjugated diene-based polymer having a high modification component is produced stably in the production process. About the method. Further, the modified conjugated diene-based polymer produced by the present invention is mainly used for tires, in which a conjugated diene-based polymer rubber is conventionally used, a modifier for impact-resistant styrene resin, It is suitably used for adhesives, asphalt modifiers, and other industrial products.

[0002]

2. Description of the Related Art In recent years, there has been an increasing demand for reduction of carbon dioxide gas emitted from automobiles and low fuel consumption due to an increase in interest in environmental issues. In order to meet such demands, the rolling resistance of tire performance has been reduced. Is being sought. As a method of lowering the rolling resistance of the tire, optimization of the structure of the tire has been considered, but the use of a less heat-generating material as the rubber composition has been performed as the most general method. . Among them, a method of modifying the terminal of a conjugated diene polymer with a functional group is becoming more common as the most typical technique. As a method of introducing a functional group to the terminal of the conjugated diene polymer, in a hydrocarbon solvent,
Polymerization of 1,3-butadiene using an organolithium catalyst,
Or after copolymerizing 1,3-butadiene and styrene,
A method of introducing a functional group by reacting a modifier capable of reacting with an active terminal with active lithium is generally used. Using these techniques, various modified conjugated diene polymers suitable for various uses have been proposed.

However, in anionic polymerization using an organolithium catalyst, impurities in the raw material, particularly water, acetylenes, allenes, etc., react with the active lithium terminal of the polymer to inactivate the active terminal. When a modified conjugated diene polymer is produced, a problem arises in that a desired amount of a functional group cannot be introduced. Therefore, dehydration and purification of monomers and solvents are important, and distillation is generally employed for dehydration and purification in industrial scale production. However, these methods cannot be said to be sufficiently effective, while on the other hand, in order to obtain a sufficient effect, a great deal of cost is required economically at present. In order to solve these problems, JP-A-57-73013 and JP-A-59-1763111 disclose that, after contact-mixing 1,3-butadiene and a hydrocarbon solvent with an organic lithium compound, polymerization is carried out. Proposed.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a method for producing a conjugated diene polymer having a highly modified component without deactivating the active terminal of the polymer. That is, an object of the present invention is to provide a method for producing a conjugated diene polymer having a high modification component by using a monomer containing a specific amount of impurities after treating it with an organometallic compound.

[0005]

Means for Solving the Problems The present inventors have conducted intensive studies on a method for producing a modified conjugated diene-based polymer in order to solve the above-mentioned problems, and have found that a monomer containing a specific amount of a specific impurity is contained in an organometallic compound. And found that a conjugated diene-based polymer having a highly modified component can be obtained, thereby completing the present invention.

That is, according to the present invention, a conjugated diene monomer is polymerized or a conjugated diene monomer is copolymerized with an aromatic vinyl monomer in a hydrocarbon solvent using an organolithium compound as an initiator. Later, a method for producing a modified conjugated diene-based polymer by reacting with a compound having a functional group capable of reacting with the active terminal of the obtained conjugated diene-based polymer,
(1) Using a monomer in which the total amount of acetylenes and allenes as impurities is less than 200 ppm based on all monomers, (2) using a monomer or a monomer and a hydrocarbon solvent in an organometallic compound After the treatment, the monomer is fed to the polymerization reactor, and (3) after the polymerization is completed, a modifier is added to remove the modified component by 6%.
0% by weight or more of a modified conjugated diene-based polymer.
2-butadiene less than 200 ppm, propadiene 10
A process for producing a modified conjugated diene-based polymer characterized by treating a monomer having a methyl acetylene content of 20 ppm or less, an ethyl acetylene content of 20 ppm or less, and a vinyl acetylene content of 20 ppm or less as acetylenes. I do.

Hereinafter, the present invention will be described in detail. As the polymerization initiator used in the present invention, an anionic polymerization initiator is used, and an organic alkali metal compound and an organic alkaline earth metal are preferable, and an organic lithium compound is particularly preferable. Organic lithium compounds include all organic lithium initiators capable of initiating polymerization, low molecular weight,
A solubilized oligomeric organolithium compound;
One having a single lithium in the molecule, one having a plurality of lithiums in one molecule, one having a carbon-lithium bond, one having a nitrogen-lithium bond, and one having a tin-lithium bond in a bonding mode of an organic group and lithium. And the like.

Specifically, n-butyllithium, sec-butyllithium, t-butyllithium are used as monoorganic lithium compounds.
Butyl lithium, n-hexyl lithium, benzyl lithium, phenyl lithium, stilbene lithium, etc.
Reaction of 1,4-dilithiobutane, a reaction product of sec-butyllithium with diisopropenylbenzene, 1,3,5-trilithiobenzene, reaction of n-butyllithium with 1,3-butadiene and divinylbenzene as polyfunctional organic lithium compounds And dimethylaminolithium, dihexylaminolithium, diisopropylaminolithium, hexamethyleneiminolithium, etc., as a compound comprising a nitrogen-lithium bond, for example, a reaction product of n-butyllithium and a polyacetylene compound.

Particularly preferred are n-butyllithium and sec-butyllithium. These organic lithium compounds are used not only as one kind but also as a mixture of two or more kinds. In the polymerization reaction, diethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, 2,2-bis (2-oxolanyl) propane or the like is used for the purpose of randomly copolymerizing an aromatic vinyl monomer with a conjugated diene-based monomer. Ethers, triethylamine,
It is also possible to add an aprotic polar compound such as amines such as tetramethylethylenediamine.

The rubbery polymer produced in the present invention is a conjugated diene polymer or a conjugated diene-aromatic vinyl copolymer. Examples of the conjugated diene monomer include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene,
Methyl-1,3-pentadiene, 1,3-heptadiene, 1,3-hexadiene and the like can be mentioned, and one kind or a combination of two or more kinds is used. Preferred monomers include 1,3-butadiene and isoprene. Examples of the aromatic vinyl monomer include styrene, p
-Methylstyrene, α-methylstyrene, vinylethylbenzene, vinylxylene, vinylnaphthalene, diphenylethylene and the like, and one kind or a combination of two or more kinds is used. Preferred monomers include styrene.

The hydrocarbon solvent used in the method for producing the modified conjugated diene polymer is a saturated hydrocarbon or an aromatic hydrocarbon, such as an aliphatic hydrocarbon such as butane, pentane, hexane or heptane; cyclopentane; Use is made of alicyclic hydrocarbons such as cyclohexane, methylcyclopentane and methylcyclohexane, aromatic hydrocarbons such as benzene, toluene and xylene, and hydrocarbons composed of mixtures thereof. When the polymer having an active lithium terminal of the present invention is a copolymer comprising a conjugated diene as described above and a monomer copolymerizable therewith, the content of the copolymerizable monomer or the copolymer The chain distribution of the copolymerizable monomer in the chain is not particularly limited. In addition, the composition distribution of the monomer capable of being copolymerized with the conjugated diene in the copolymer chain may be uniform in the molecular chain, or may be unevenly distributed in the molecular chain, It may exist as a block.

The impurities in the monomer used in the present invention include:
The total amount of acetylenes and allenes is less than 200 ppm. Even if a monomer containing impurities of 200 ppm or more is treated with an organometallic compound, the reaction products of acetylenes and metal compounds of allenes further deactivate the active terminal of the polymer in the polymerization system. This is not preferred. More specifically, it is necessary to use a conjugated diene monomer containing 20 ppm or less of methylacetylene, 20 ppm or less of ethylacetylene, 20 ppm or less of vinylacetylene, and 80 ppm or less of phenylacetylene as acetylenes. If these exceed 20 ppm,
The compound reacted with the organometallic compound further deactivates the active terminal of the polymer in the polymerization system, which is not preferable. Preferably, methyl acetylene is 10 ppm or less, ethyl acetylene is 10 ppm or less, and vinyl acetylene is 10 ppm or less. More preferably, methyl acetylene is 5 ppm or less, ethyl acetylene is 5 ppm or less, vinyl acetylene is 5 ppm or less, and phenyl acetylene is 40 pp.
m or less.

[0013] The content of phenylacetylene in the aromatic vinyl monomer is preferably 80 ppm or less. More preferably, it is 40 ppm or less. It is necessary to use a conjugated diene monomer containing less than 200 ppm of 1,2-butadiene and 100 ppm or less of propadiene as allenes. If a conjugated diene-based monomer containing impurities exceeding this amount is treated with an organometallic compound, the reaction product further deactivates the active terminal of the polymer in the polymerization system, which is not preferable. Preferably, 1,2-butadiene is 100 ppm or less and propadiene is 50 ppm or less, and more preferably, 1,2-butadiene is 30 ppm or less and propadiene is 10 ppm or less.

Examples of the organometallic compound used for treating the monomer include an organic lithium compound, an organic sodium compound,
Organic magnesium compounds and the like, specifically, n
-Butyl lithium, sec-butyl lithium, t-butyl lithium, n-hexyl lithium, benzyl lithium, phenyl lithium, stilbene lithium, sodium naphthalene, dibutyl magnesium and the like.
In order to efficiently react with impurities, the organometallic compound can be activated by using a polar compound such as ethers, amines, phosphines and sulfides in combination.

The polymerization reaction is carried out after treating a monomer or a mixture of a monomer and a hydrocarbon solvent with an organometallic compound. As a treatment method, a method is generally used in which a monomer is contacted and mixed with an organometallic compound in an amount corresponding to an impurity before the monomer is introduced into a reactor. Further, the conjugated diene-based polymer becomes a product as a solid rubber after desolvation of a rubber solution obtained by polymerizing the monomer. The hydrocarbon solvent used for the polymerization is recovered and purified in the production process of the conjugated diene polymer and then reused. However, in the solvent recovery step, acetylenes in the monomer,
In some cases, impurities of allenes are mixed in a hydrocarbon solvent and the impurities cannot be completely removed even after purification. Therefore, in some cases, it is necessary to treat allenes and acetylenes in the hydrocarbon solvent with the organometallic compound. The temperature of the contact mixing is in the range of -10 to 50C, and the polymerization addition rate is preferably 10% or less. If the contact mixing temperature is lower than −10 ° C., the reaction between the organometallic compound and the impurities is insufficient, and the inactivation of the impurities is also insufficient. Also,
If the contact mixing temperature exceeds 50 ° C., the polymerization conversion rate exceeds 10% before the polymerization is carried out, and a gel is easily formed at the mixing point, which is not preferable. Further, the contact mixing time is preferably a short time of less than 5 minutes.

By using these methods alone or in combination, it becomes possible to greatly reduce the deactivation of the active terminal during polymerization due to impurities contained in the monomer. The denaturation reaction can be performed efficiently. The polymerization reaction is carried out at a polymerization temperature of 50 to 150 ° C. and a final polymer concentration of 5 to 30% by weight, and the polymerization temperature is determined by taking into account that the polymerization is an exothermic reaction. And the solvent feed temperature, monomer concentration, and cooling or heating from outside the reactor. The polymerization is preferably carried out at 70 to 120 ° C, more preferably at 80 to 100 ° C. The denaturation reaction is
It is carried out at a temperature above 80 ° C., preferably below 120 ° C. Any modifier can be used as long as it can react with the active terminal of the polymer, and examples thereof include the following.

(1) Polyfunctional compounds having two or more epoxy groups in the molecule, specifically, polyglycidyl ethers of polyhydric alcohols such as ethylene glycol diglycidyl ether and glycerin triglycidyl ether, and diglycidylated bisphenol A Polyglycidyl ethers of aromatic compounds having two or more phenol groups, such as 1,
Polyepoxy compounds such as 4-diglycidylbenzene, 1,3,5-triglycidylbenzene, polyepoxidized liquid polybutadiene, 4,4'-diglycidyl-diphenylmethylamine, 4,4'-diglycidyl-dibenzylmethylamine and the like Epoxy-containing tertiary amines, diglycidylaniline, diglycidylorthotoluidine, tetraglycidylmethaxylenediamine, tetraglycidylaminodiphenylmethane, tetraglycidyl-p-phenylenediamine, diglycidylaminomethylcyclohexane, tetraglycidyl-1,3-bis And diglycidylamino compounds such as aminomethylcyclohexane.

(2) N-substituted amino aldehydes, N-
A compound selected from substituted aminothioaldehydes, N-substituted aminoketones, N-substituted aminothioketones, and compounds having the following structure in the molecule:

Embedded image (In the formula, M represents an oxygen atom or a sulfur atom.)

Specifically, 4-dimethylaminobenzophenone, 4-diethylaminobenzophenone, 4-di-
t-butylaminobenzophenone, 4-diphenylaminobenzophenone, 4,4'-bis (dimethylamino)
Benzophenone, 4,4'-bis (diethylamino) benzophenone, 4,4'-bis (di-t-butylamino) benzophenone, 4,4'-bis (diphenylamino) benzophenone, 4,4'-bis (divinylamino) N-substituted amino ketones such as benzophenone, 4-dimethylaminoacetophenone, 4-diethylaminoacetophenone, 1,3-bis (diphenylamino) -2-propanone, and 1,7-bis- (methylethylamino) -4-heptanone And corresponding N-substituted aminothioketones; N-substituted aminoaldehydes such as 4-diethylaminobenzaldehyde and 4-divinylaminobenzaldehyde, and corresponding N-substituted aminothioaldehydes;

N-methyl-β-propiolactam, N-
t-butyl-β-propiolactam, N-phenyl-β
-Propiolactam, N-methoxyphenyl-β-propiolactam, N-naphthyl-β-propiolactam,
N-methyl-2-pyrrolidone, Nt-butyl-2-pyrrolidone, N-phenyl-pyrrolidone, N-methoxyphenyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, N-benzyl-2-pyrrolidone, N -Naphthyl-2
-Pyrrolidone, N-methyl-5-methyl-2-pyrrolidone, N-methyl-3,3'-dimethyl-2-pyrrolidone, Nt-butyl-3,3'-dimethyl-2-pyrrolidone, N-phenyl -3,3'-Dimethyl-2-pyrrolidone, N-methyl-2-piperidone, Nt-butyl-
2-piperidone, N-phenyl-piperidone, N-methoxyphenyl-2-piperidone,

N-vinyl-2-piperidone, N-benzyl-2-piperidone, N-naphthyl-2-piperidone,
N-methyl-3,3'-dimethyl-2-piperidone, N
-Phenyl-3,3'-dimethyl-2-piperidone, N
-Methyl-ε-caprolactam, N-phenyl-ε-caprolactam, N-methoxyphenyl-ε-caprolactam, N-vinyl-ε-caprolactam, N-benzyl-ε-caprolactam, N-naphthyl-ε-caprolactam, N- N such as methyl-ω-laurylolactam, N-phenyl-ω-laurylolactam, Nt-butyl-laurylolactam, N-vinyl-ω-laurylolactam, N-benzyl-ω-laurylolactam -Substituted lactams and their corresponding thiolactams;

1,3-dimethyl-2-imidazolidinone, 1,3-diethyl-2-imidazolidinone, 1,3
-Dipropyl-2-imidazolidinone, 1-methyl-3
-Ethyl-2-imidazolidinone, 1-methyl-3-propyl-2-imidazolidinone, 1-methyl-3-ethyl-2-imidazolidinone, 1-methyl-3- (2-ethoxyethyl)- Examples include N-substituted ethylene ureas such as 2-imidazolidinone and 1,3-dimethyl-3,4,5,6-tetrahydropyrimidinone and corresponding N-substituted thioethylene ureas.

(3) A compound selected from benzophenones or thiobenzophenones having at least one amino group, alkylamino group or dialkylamino group, specifically, 4,4'-bis ( Dimethylamino) -benzophenone, 4,4'-bis (diethylamino) -benzophenone, 4,4'-bis (dibutylamino) -benzophenone, 4,4'-diaminobenzophenone, 4-dimethylaminobenzophenone and the like and their corresponding Examples include benzophenone and thiobenzophenone having at least one amino group, alkylamino group or dialkylamino group on one or both benzene rings, such as thiobenzophenone.

(4) General formula, R _n MX _4-n (where R is an alkyl group, alkenyl group, cycloalkenyl group or aromatic hydrocarbon group, M is a silicon or tin atom, and X is Is a halogen atom, and n is an integer of 0 to 3), and is a silicon compound or a tin compound compound selected from the compounds represented by the following formulas. Specifically, the silicon compound is tetrachlorosilicon or tetrabromosilicon. , Methyltrichlorosilicon, butyltrichlorosilicon, dichlorosilicon, bistrichlorosilylsilicon and the like are used. Silyl tin or the like is used.

[0025] (5) In ^{_{formula, X n M (OR 1)}} m R 2 4-mn ( where wherein R ^1, R ² is an alkyl group, an alkenyl group,
A cycloalkenyl group or an aromatic hydrocarbon group, M represents a silicon or tin atom, X represents a halogen atom, n is an integer of 0 to 2, m is an integer of 1 to 4, and the sum of m and n is 2 to 4
It is. ), Specifically, dimethoxydimethylsilane, diphenoxydimethylsilane, diethoxydiethylsilane, triphenoxymethylsilane, triphenoxyvinylsilane, trimethoxyvinylsilane, triethoxyvinylsilane, and triethoxyvinylsilane. (2-methylbutoxy) ethylsilane, tri (2-methylbutoxy) vinylsilane, triphenoxyphenylsilane,

Tetraphenoxysilane, tetraethoxysilane, tetramethoxysilane, tetrakis (2-ethylhexyloxy) silane, phenoxydivinylchlorosilane, methoxybiethylchlorosilane, diphenoxymethylchlorosilane, diphenoxyphenyliodosilane, diethoxymethylchlorosilane, Dimethoxymethylchlorosilane, trimethoxychlorosilane, triethoxychlorosilane, triphenoxychlorosilane, tris (2-ethylhexyloxy) chlorosilane, phenoxymethyldichlorosilane, methoxyethyldichlorosilane, ethoxymethyldichlorosilane, phenoxyphenyldiiodosilane, diphenoxydichlorosilane , Dimethoxydichlorosilane, bis (2-methylbutoxy) dibromosilane, (2-methylbutoxy) dichlorosilane, diethoxy dichlorosilane, methoxy trichlorosilane, ethoxy trichlorosilane, phenoxy trichlorosilane, (2-ethylhexyl oxy) trichlorosilane, and (2-methylbutoxy) trichlorosilane and the like.

(6) Compounds selected from isocyanate compounds or isothiocyanate compounds. Specifically, as the isocyanate compound, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate,
Diphenylmethane diisocyanate, naphthalene diisocyanate, tolidine diisocyanate, triphenylmethane triisocyanate, p-phenylene diisocyanate, tris (isocyanato-phenyl) thiophosphate, xylylene diisocyanate, benzene-1,2,4
Triisocyanate, naphthalene-1,2,5,7-tetraisocyanate, naphthalene-1,3,7-triisocyanate, phenyl isocyanate, hexamethylene diisocyanate, methylcyclohexane diisocyanate,
Phenyl-1,4-diisothiocyanate and the like.

Preferably, aromatic diisocyanates or triisocyanates or dimers and trimers of various aromatic isocyanate compounds and aromatic isocyanates such as adducts obtained by reacting the aromatic isocyanates with polyols and polyamines. A nate compound is used. More preferably, aromatic polyisocyanate compounds such as 2,4-tolylene diisocyanate, diphenylmethane diisocyanate, and naphthalene diisocyanate are exemplified.

(7) R ¹ _m Si (OR ² ) _n X _(4-mn) (wherein R ¹ is a substituent having an epoxy group or an unsaturated carbonyl group, X is an alkyl group, a halogen atom,
R ² represents a group selected from aliphatic, alicyclic and aromatic hydrocarbon groups having 1 to 20 carbon atoms. m is an integer of 1 to 3,
n represents an integer of 1 to 3, and m + n is 2
Represents an integer of from 4 to 4. ), Specifically, for example, γ-glycidoxyethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxy Butyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltripropoxysilane, γ-glycidoxypropyltributoxysilane, γ-glycidoxypropyltriphenoxysilane, γ-glycidoxysilane Propylmethyldimethoxysilane,

Γ-glycidoxypropylethyldimethoxysilane, γ-glycidoxypropylethyldiethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldipropoxysilane, γ-glycid Xypropylmethyldibutoxysilane, γ-glycidoxypropylmethyldiphenoxysilane, γ-glycidoxypropyldimethylmethoxysilane, γ-glycidoxypropyldiethylethoxysilane, γ-glycidoxypropyldimethylethoxysilane, γ-glycidoxypropyldimethylethoxysilane Glycidoxypropyldimethylphenoxysilane, γ-glycidoxypropyldiethylmethoxysilane, γ-glycidoxypropylmethyldiisopropeneoxysilane, bis (γ-glycidoxypropyl) dimethoxysilane,

Bis (γ-glycidoxypropyl) diethoxysilane, bis (γ-glycidoxypropyl) dipropoxysilane, bis (γ-glycidoxypropyl) dibutoxysilane, bis (γ-glycidoxypropyl) ) Diphenoxysilane, bis (γ-glycidoxypropyl) methylmethoxysilane, bis (γ-glycidoxypropyl) methylethoxysilane, bis (γ-glycidoxypropyl) methylpropoxysilane, bis (γ-glycid (Xypropyl) methylbutoxysilane, bis (γ-glycidoxypropyl) methylphenoxysilane, tris (γ-glycidoxypropyl) methoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-methacryloxymethyltrimethoxysilane, γ-methac Riloxyethyltriethoxysilane,

Bis (γ-methacryloxypropyl) dimethoxysilane, tris (γ-methacryloxypropyl)
Methoxysilane, β- (3,4-epoxycyclohexyl) ethyl-trimethoxysilane, β- (3,4-epoxycyclohexyl) ethyl-triethoxysilane, β-
(3,4-epoxycyclohexyl) ethyl-tripropoxysilane, β- (3,4-epoxycyclohexyl) ethyl-tributoxysilane, β- (3,4-epoxycyclohexyl) ethyl-triphenoxysilane,
β- (3,4-epoxycyclohexyl) propyl-trimethoxysilane, β- (3,4-epoxycyclohexyl) ethyl-methyldimethoxysilane, β- (3,4
-Epoxycyclohexyl) ethyl-ethyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyl-ethyldiethoxysilane,

Β- (3,4-epoxycyclohexyl)
Ethyl-methyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethyl-methyldipropoxysilane, β- (3,4-epoxycyclohexyl) ethyl-
Methyldibutoxysilane, β- (3,4-epoxycyclohexyl) ethyl-methyldiphenoxysilane, β-
3,4-epoxycyclohexyl) ethyl-dimethylmethoxysilane, β- (3,4-epoxycyclohexyl) ethyl-diethylethoxysilane, β- (3,4-
Epoxycyclohexyl) ethyl-dimethylethoxysilane, β- (3,4-epoxycyclohexyl) ethyl
-Dimethylpropoxysilane, β- (3,4-epoxycyclohexyl) ethyl-dimethylbutoxysilane, β
-(3,4-epoxycyclohexyl) ethyl-dimethylphenoxysilane, β- (3,4-epoxycyclohexyl) ethyl-diethylmethoxysilane, β- (3
4-epoxycyclohexyl) ethyl-methyldiisopropeneoxysilane.

(8) a compound selected from organosiloxane compounds represented by the following general formula:

Embedded image (Wherein X _{1 to} X ₈ are each independently an alkoxyl group, vinyl group, chlorine atom, bromine atom, iodine atom or a hydrocarbon group having at least one of them; a hydrocarbon group having an epoxy group; a carbonyl group A hydrocarbon group having:
A hydrogen atom; an alkyl group; or a phenyl group, and m and n are each independently an integer of 0 to 100. However, m and n do not become 0 at the same time. Specifically, for example, diglycidyldimethylsiloxane, dimethyl (methoxy-methylsiloxane) polydimethylsiloxane,
Dimethyl (acetoxy-methyl siloxane) polydimethyl siloxane, diglycidyl polysiloxane, dichloro polydimethyl siloxane and the like can be mentioned.

(9) a compound selected from organosiloxane compounds represented by the following general formula:

Embedded image (Wherein, R _{1 to} R ₃ are an alkyl group, an alkenyl group, a cycloalkenyl group or an aromatic hydrocarbon group, and m and n are each independently an integer of 0 to 100.
Do not become 0 at the same time. ) Specific examples include polymethoxydimethylsiloxane, polyethoxydimethylsiloxane, polymethoxydiethylsiloxane, polyethoxydiethylsiloxane, and polybutoxydimethylsiloxane.

These modifiers are preferably reacted in a molar ratio of more than 0.2 mol based on the active terminal of the polymer and 5 times or less based on the active terminal of the polymer. In the case of the active terminal of a polymer polymerized with a monofunctional initiator, 0.2
If it is less than mol, the modified component of the present invention does not contain more than 60% by weight. On the other hand, when the molar ratio exceeds 5 times, the amount of the unreacted modifier increases, and the performance is rather deteriorated.

The modified conjugated diene polymer produced in the present invention has a modified component content of 60% by weight of the whole polymer.
Needs to be exceeded. Preferably, it is 70% by weight or more. When the content of the modifying component is small, the effect of the functional group is not sufficiently exhibited. The content of the denatured component can be measured by chromatography capable of separating the denatured component and the non-denatured component. As a method for this chromatography, a GPC column using a polar substance such as silica which adsorbs the denatured component as a filler is used, and a method of quantification using an internal standard of a non-adsorbed component, a method of quantifying a polymer before denaturation and a method of There is a method of measuring the GPC of a polymer and calculating the amount of a modified portion based on a change in the shape and molecular weight of the polymer.

The modified conjugated diene-based polymer of the present invention may contain various additives as required, for example, inorganic fillers such as calcium carbonate, magnesium carbonate, zinc oxide, titanium oxide, clay, talc, glass beads, glass fibers, and the like. Organic reinforcing agents such as carbon black, organic fibers such as carbon fiber and synthetic fiber, adhesives such as coumarone indene resin and terpene resin, organic peroxides, inorganic peroxides,
Mix appropriate amounts of crosslinking agents such as sulfur, paraffinic, naphthenic, and aroma oils, various pigments, dyes, flame retardants, antistatic agents, lubricants, plasticizers, other extenders, and mixtures thereof. It is also possible to use.

The modified conjugated diene polymer of the present invention is useful as a rubber composition for tires. When used as a rubber composition for tires, the modified conjugated diene-based polymer of the present invention may be used as an extender oil for rubber, reinforcing silica, and, if necessary, a silane coupling agent, reinforcing carbon black, and other additives. Is blended. This mixture is kneaded using a known closed kneader or the like, and further a vulcanizing agent and a vulcanization accelerator are added, and the mixture is kneaded using a known kneader such as an internal mixer or a mixing roll. By vulcanizing, a rubber composition excellent in all of processability, strength characteristics, low rolling resistance and wet skid resistance is provided.
Further, the modified conjugated diene-based polymer of the present invention is useful as a toughening agent for impact-resistant styrene-based resins. Usually, as a method for producing an impact-resistant styrenic resin, a modified conjugated diene-based polymer is dissolved in a mixture with an aromatic vinyl monomer or a copolymerizable monomer so that a shear stress is applied to the rubber solution. A method of performing graft polymerization by a bulk polymerization method, a bulk suspension polymerization method, or a solution polymerization method with stirring is preferable.

The modified conjugated diene polymer of the present invention is also useful as a material for a hot melt pressure-sensitive adhesive composition having excellent pressure-sensitive adhesive properties. When used as a hot melt pressure-sensitive adhesive composition, a pressure-sensitive adhesive resin, a softening agent, and a reinforcing resin can be blended with the modified conjugated diene-based polymer of the present invention. The pressure-sensitive adhesive resin has been conventionally used as a tackifier in a hot-melt pressure-sensitive adhesive. For example, a coumarone-indene resin, a phenol resin, pt-butylphenol.
Acetylene resin, phenol / formaldehyde resin,
Terpene / phenol resin, polyterpene resin, xylene / formaldehyde resin, synthetic polyterpene resin, aromatic hydrocarbon resin, aliphatic cyclic hydrocarbon resin, oligomer of monoolefin and diolefin, hydrogenated hydrocarbon resin, hydrocarbon-based tackification Resin, polybutene, polyhydric alcohol ester of rosin, hydrogenated rosin, hydrogenated wood rosin, ester of hydrogenated rosin with monoalcohol or polyhydric alcohol, turpentine tackifier and the like.

The softener includes petroleum softener, paraffin, vegetable oil softener, plasticity and the like. Polystyrene, polyethylene, polypropylene ethylene-propylene copolymer, ethylene-butene copolymer, ethylene-vinyl acetate copolymer, as well as relatively low molecular weight thermoplastic polyester resin, polyamide resin, polyphenylene ether as reinforcing resin A thermoplastic resin such as a system resin can be used.

The modified conjugated diene polymer of the present invention can be used for road pavement, waterproofing, rust prevention, automobile undercoating, by appropriately selecting the ratio of the modified conjugated diene polymer and asphalt. It can be used for roofing, pipe coating, joint applications, etc. In particular, it is useful as a block copolymer for solving the problems of asphalt containing a conventional block copolymer, such as a melt viscosity that is too high and phase separation during storage. Examples of the asphalt include straight asphalt, semi-blown asphalt, blown asphalt, tar, pitch, and cutback asphalt to which oil is further added, and these may be arbitrarily mixed and used.

The asphalt composition may contain optional additives in optional amounts as needed. Types of additives include clay, talc, calcium carbonate, zinc oxide, inorganic fillers such as glass beads, crushed stone,
Aggregates such as gravel and sand; fibrous reinforcing materials such as glass fiber and asbestos; organic reinforcing agents such as carbon black;
Tackifying resins such as indene resin and terpene resin, softening agents such as paraffinic, naphthenic and aroma oils,
Examples include thermoplastic resins such as polyolefin resins, polystyrene resins, and polyvinyl chloride resins, and synthetic rubbers such as natural rubber, polybutadiene rubber, styrene-butadiene rubber, and nitrile rubber.

When the modified conjugated diene polymer of the present invention is used for shoe soles, automobile parts, industrial parts, etc., an inorganic filler and / or an organic filler, a softener, and a thermoplastic resin may be blended. it can. Examples of the inorganic filler and / or the organic filler include calcium carbonate, clay, silica, zinc white, magnesium carbonate, magnesium silicate, talc, diatomaceous earth, dolomite, mica powder, aluminum sulfate, barium sulfate, graphite, and glass fiber. ,Carbon black,
Examples include high styrene resin, cumarone / indene resin, phenol / formaldehyde resin, modified melamine resin, petroleum resin, lignin, wood flour, carbon fiber and the like. Examples of the softener include lubricating oils, paraffinic process oils, naphthenic process oils, aroma-based process oils, paraffin, vaseline, asphalt, vegetable oils (castor oil, cottonseed oil, rapeseed oil, soybean oil, etc.), rosin, fatty acids, and the like. Can be

As the thermoplastic resin, olefin resin, styrene resin, acrylate resin, vinyl chloride resin, polyamide resin, polyester resin, polycarbonate resin, polyphenylene ether resin,
Examples include polyphenylene sulfide-based resin, polyacetal-based resin, and polyurethane-based resin. Among them, olefin resins such as polyethylene, polypropylene, and ethylene / propylene copolymer, and styrene resins such as polystyrene and rubber-modified impact-resistant polystyrene are preferably used.

Further, the modified conjugated diene-based polymer of the present invention
It can also be used as a modifier for the various thermoplastic resins described above. When the above-mentioned composition is produced by using the block copolymer of the present invention, various mixing apparatuses used for mixing ordinary polymer substances depending on the composition of the components, for example, a single-screw or multi-screw extruder , Mixing roll,
It can be prepared by using a Banbury mixer, a kneader or the like, and is preferably mixed in a molten state. Further, the composition can also be obtained by, for example, a method in which a solution of each component is mixed and the solvent is removed by heating. Compositions obtained by adding various additives to the modified conjugated diene-based polymer of the present invention can be formed into sheets, foams, films, and various shapes by any conventionally known molding methods such as extrusion molding, injection molding, and hollow molding. Can be easily molded into a wide variety of practically useful products such as injection molded products, hollow molded products, compressed air molded products, footwear, electric wire cables,
In addition to food packaging containers, it can be used for various automotive parts, industrial supplies, etc.

Hereinafter, the present invention will be described specifically with reference to Examples and Comparative Examples, but these do not limit the scope of the present invention in any way.

Examples 1 to 3 An inner volume of 10 liters, an inlet at the bottom,
An autoclave having a stirrer and a jacket having an outlet at the head was connected in series as a reactor, and 16.38 g of 1,3-butadiene (BB-1) shown in Table 1 was obtained.
After mixing styrene (SS-2) at 8.82 g / min and n-hexane at 132.3 g / min, the mixed solution is passed through a dehydration column filled with activated alumina to remove impurities. 0.0046 n-butyllithium
After mixing in a static mixer at a speed of g / min,
It is continuously supplied from the bottom of the first reactor using a metering pump, and 2,2-bis (2-oxolanyl) propane is used as a polar substance at a rate of 0.028 g / min. Lithium was directly supplied to the reactor at a rate of 0.0070 g / min, and the internal temperature of the reactor was maintained at 86 ° C. The polymer solution was continuously withdrawn from the reactor head and supplied to the second reactor.

After the state of the first reactor was stabilized, the Mooney viscosity of the obtained polymer before the modification reaction was 55 at 100 ° C. With the temperature of the second reactor kept at 80 ° C., tetraglycidyl-1,3-bisaminomethylcyclohexane was added from the bottom of the reactor at a rate of 0.009 g / min (equivalent ratio to active lithium = 0.9). Then, a denaturation reaction was performed. An antioxidant was continuously added to the polymer solution to terminate the modification reaction, and then the solvent was removed to obtain a styrene-butadiene copolymer having a desired modified component. Further, 37.5 parts by weight of an aromatic oil (X-140 manufactured by Japan Energy Co., Ltd.) was added to the polymer solution to obtain an oil-extended rubber of Rubber Sample A shown in Table 2 by adding 37.5 parts by weight per 100 parts by weight of the polymer. In addition, a butadiene species and BuLi to be treated with impurities are obtained by the same continuous polymerization method as that for obtaining sample A.
Samples B and C having different structures were obtained by changing the amount, the amount of BuLi used for the polymerization, and the amount of the modifier.

[0049]

EXAMPLES 4-5 An autoclave having an internal volume of 10 liters and equipped with a stirrer and a temperature controllable jacket was used as a reactor, and 1,3-butadiene (BB-1) shown in Table 1 was used. 645 g of butadiene treated with 0.15 g of n-butyllithium, styrene (SS-2)
280 g, cyclohexane 5500 g, and 2,2-bis (2-oxolanyl) propane as a polar substance.
70 g was put into the reactor, and the temperature inside the reactor was maintained at 30 ° C. 0.85 g of n-butyllithium as a polymerization initiator
Was fed to the reactor. After the start of the reaction, the temperature inside the reactor gradually increased due to the heat generated by the polymerization. From 7 minutes to 12 minutes after the addition of the polymerization initiator, 75 g of butadiene treated with 0.02 g of n-butyllithium was supplied at a rate of 15 g / min.

The final reactor temperature reached 75 ° C.
After the completion of the polymerization reaction, a part of the polymer solution was collected. The Mooney viscosity of the polymer before the modification reaction measured after removing the solvent is 1
It was 7 when measured at 00 ° C. 1.2 g of tetraglycidyl-1,3-bisaminomethylcyclohexane was added as a denaturant to the reactor, and the mixture was kept at 75 ° C. for 5 minutes to carry out a denaturation reaction. After adding an antioxidant to this polymer solution, the solvent was removed, and a sample D having a target modified component shown in Table 2 was obtained. Further, different samples E shown in Table 2 were obtained by changing the butadiene species, the amount of BuLi to be subjected to the impurity treatment, the amount of BuLi used for the polymerization, and the amount of the modifier in the same manner as the sample D was obtained.

COMPARATIVE EXAMPLE Sample F having the modified components shown in Table 2 in the same manner as in Example 1 except that the raw material was not treated with n-butyllithium.
I got In the same manner as in Example 4, Sample G having the modified components shown in Table 2 was obtained.

The analysis of the sample was performed by the following method. 1) Amount of bound styrene A sample was prepared as a chloroform solution, and the amount of bound styrene [S] was determined by the absorption of UV at 254 nm by the phenyl group of styrene.
(Wt%) was measured. 2) Microstructure of butadiene portion The sample was prepared as a carbon disulfide solution, the infrared spectrum was measured in the range of 600 to 1000 cm ^-1 using a solution cell, and the microstructure of the butadiene portion was calculated from the predetermined absorbance according to the Hampton formula. I asked.

3) Mooney viscosity According to JIS-K-6300, 100 ° C., 4 minutes after preheating for 1 minute
The viscosity after one minute was measured. 4) Molecular weight and molecular weight distribution A chromatogram was measured using GPC using three columns connected with a polystyrene-based gel as a filler, and the molecular weight and molecular weight distribution were calculated from a calibration curve using standard polystyrene.

523) Modification rate By applying the property of adsorbing the denatured component to a GPC column using silica gel as a filler, the polystyrene gel (5) described above for the sample and the sample solution containing low-molecular-weight internal standard polystyrene was used. Showa Denko's (Shodex) GP
C and silica-based column GPC (Zorba manufactured by DuPont)
Both chromatograms of x) were measured, and the amount of adsorption to the silica column was measured from the difference between them to determine the denaturation rate.

[0054]

REFERENCE EXAMPLE A rubber compound was obtained by the following kneading method using the samples shown in Table 2 as raw rubbers and the compounds shown in Table 3. [Kneading method] Using a Banbury-type hermetic kneader (with an internal capacity of 1.7 liters) equipped with a temperature controller using external circulating water, the first stage kneading was performed at a filling rate of 65% and a rotor rotation speed of 66/77 rpm. Under the conditions, a raw rubber, a filler (silica and carbon black), an organic silane coupling agent, an aromatic oil, zinc white, and stearic acid were kneaded. (The kneading procedure is shown in Table 4).

Next, as the second stage kneading, the mixture obtained above was cooled to room temperature, an antioxidant was added, and the mixture was kneaded again to improve the dispersion of silica. Also in this case, the discharge temperature was adjusted according to the temperature of the mixer. After cooling, as a third stage kneading, sulfur and a vulcanization accelerator were kneaded with an open roll set at 70 ° C. This was molded and vulcanized with a vulcanizing press at 160 ° C. for a predetermined time, and the properties of the following tire properties were measured. Table 5 shows the results.

1) Bound rubber amount: After completion of the second-stage kneading, 0.2 g of the sampled composition was cut into approximately 1 mm squares, placed in a Harris basket (made of 100 mesh wire mesh), and measured for weight. After being immersed in toluene for 24 hours, the weight was measured, and the amount of rubber bonded to the filler was calculated from the amount of undissolved components to obtain the bound rubber amount. 2) Formula Mooney viscosity: Using Mooney viscometer, J
According to IS-K-6300, preheating for 1 minute at 130 ° C, 2 minutes
Measure viscosity 4 minutes after rotation. If the Mooney viscosity exceeds 80, workability is poor. If the Mooney viscosity is 30 or less, the adhesion becomes large and it becomes difficult to process.

3) Tensile strength: Measured by the tensile test method of JIS-K-6251. 4) Fuel economy characteristics: Tested with Tan δ at 50 ° C. Measured at a frequency of 10 Hz, a strain of 3%, and 50 ° C. by a torsion method using an Ares viscoelasticity tester manufactured by Rheometrics.
The smaller the number, the better the fuel economy performance. 5) Wet skid resistance performance: Tan δ at 0 ° C.
Test with. Rheometrics, Ares viscoelasticity tester, frequency 10Hz, strain 3%, 0
Measured in ° C. The higher the number, the better the wet skid resistance performance.

As is clear from Table 2, a modified conjugated diene-based polymer having a high modification rate can be obtained even when a butadiene monomer and a styrene monomer which are high in allenes and acetylenes are treated with n-butyllithium. Absent. Further, as is apparent from Table 5, the vulcanized rubber compositions using the rubbery polymers within the scope of the present invention of Examples 1 to 4 were mixed with the composition of Comparative Example 1 in the same silica-containing composition. In comparison, it can be seen that it has good fuel economy and good wet skid properties.

[0059]

[Table 1]

[0060]

[Table 2]

[0061]

[Table 3]

[0062]

[Table 4]

[0063]

[Table 5]

[0064]

The modified conjugated diene polymer produced by the method of the present invention is a modified conjugated diene polymer having a high modification component. Also, by using the modified conjugated diene-based polymer in a specific composition containing a reinforcing silica filler, a vulcanized rubber composition for a tire tread having excellent strength properties, workability, fuel saving performance, and grip performance is provided. You. Furthermore, it can be used for resin modification, adhesives, asphalt modifiers, footwear, electric wire cables, food packaging containers, as well as various automobile parts, industrial supplies, and the like.

 ────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Yuichi Kitagawa 1-3-1 Yoko, Kawasaki-ku, Kawasaki-shi, Kanagawa F-term in Asahi Kasei Corporation 4J015 DA02 4J100 AB00Q AB02Q AB03Q AB04Q AB13Q AS01P AS02P AS03P AS04P CA01 CA04 CA27 CA31 FA00 FA08 FA19 HA61 HC39 HC47 HC51 HC63 HC69 HC77 HC78 HC80 HC85 JA05 JA28 JA29 JA43 JA57 JA59 JA67

Claims (3)

[Claims] 1. A method comprising: obtaining a conjugated diene monomer in a hydrocarbon solvent using an organolithium compound as an initiator, or copolymerizing a conjugated diene monomer and an aromatic vinyl monomer in a hydrocarbon solvent. A modified conjugated diene-based polymer by reacting the conjugated diene-based polymer with a compound having a functional group capable of reacting with an active terminal of the conjugated diene-based polymer, wherein (1) the total amount of acetylenes and allenes as impurities is (2) After treating a monomer or a monomer and a hydrocarbon solvent with an organometallic compound using a monomer that is less than 200 ppm based on all monomers, feed the monomer to a polymerization reactor. (3) A method for producing a modified conjugated diene-based polymer, characterized in that a modifier is added after polymerization is completed so that the content of the modifying component is 60% by weight or more. 2. Allenes include less than 200 ppm of 1,2-butadiene and 100 ppm or less of propadiene, and 20 ppm of methylacetylene as acetylenes.
2. The method for producing a modified conjugated diene polymer according to claim 1, wherein a monomer having an ethylacetylene content of 20 ppm or less and a vinylacetylene content of 20 ppm or less is treated. 3. The method for producing a modified conjugated diene polymer according to claim 1, wherein a mixture of a hydrocarbon solvent and a monomer is treated with an organometallic compound.