JPH0833846A - Multiple catalyst for olefin hydrogenation and production of hydrogenated conjugated diene based polymer - Google Patents

Abstract

PURPOSE:To obtain an extrahigh pressure hydrogenation catalyst showing the activity in an extremely small quantity with excellent reproducibility in hydrogenation reaction by reducing a specific titanocene compound with a specific reducing agent under the presence of a specific double bond-containing polymer and, after that, adding a polar compound thereinto to prepare for obtaining the catalyst. CONSTITUTION:At least one kind of the titanocene compound expressed by the formula (each of R<1> and R<2> represents a group selected from a 1-12C hydrocarbon group, an aryloxy group, an alkoxyl group, a halogen group and a carbonyl group and they may same be or different from each other. Cp represents a cyclopentadiene group.) is reduced with one kind of the reducing agent selected from an Li, Na, K, Mg, Ba, Zn, Al or Ca-containing compound under the presence of the olefinic unsaturated double bond containing polymer 0.3-1 in the ratio of the quantity of branched olefinic unsaturated double bond to total quantity of olefinic unsaturated double bond. After that, the polar compound such as an alcohol compound or an ether compound is added and prepared.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composite catalyst for hydrogenating an olefin compound and an olefinic compound in a conjugated diene polymer or a copolymer of a conjugated diene and a vinyl aromatic hydrocarbon using the catalyst. The present invention relates to a method for producing a hydrogenated conjugated diene polymer by selectively hydrogenating a saturated double bond.

[0002]

As a hydrogenation catalyst for a compound having an olefinically unsaturated double bond, a heterogeneous catalyst and a homogeneous catalyst are generally known. The former heterogeneous catalyst is widely used industrially, but is generally less active than the homogeneous catalyst, and requires a large amount of catalyst to carry out the desired hydrogenation reaction. It will be uneconomical because it is given. On the other hand, the latter homogeneous catalyst generally has a high activity as compared with a heterogeneous system because the hydrogenation usually proceeds in a homogeneous system, which requires less catalyst and has the characteristic that it can be hydrogenated at a lower temperature and a lower pressure. ,
Catalyst preparation is complicated and the stability of the catalyst itself is not sufficient,
It also has a drawback that it is inferior in reproducibility and easily causes undesirable side reactions. In addition, when hydrogenating an olefinically unsaturated double bond substituted with an alkyl group having steric hindrance, sufficient hydrogenation activity has not been obtained. Therefore, under the present circumstances, there is a strong demand for the development of a hydrogenation catalyst which has high activity and is easy to handle.

On the other hand, in a polymer containing an olefinically unsaturated double bond, the unsaturated double bond is advantageously used for vulcanization and the like, while the double bond is stable in heat resistance and oxidation resistance. It has the disadvantage of being inferior in sex. These inferior instabilities are significantly improved by hydrogenating the polymer to eliminate unsaturated double bonds in the polymer chain. However, in the case of hydrogenating a polymer, compared with the case of hydrogenating a low-molecular compound,
Hydrogenation becomes difficult due to the influence of the viscosity of the reaction system and the steric hindrance of the polymer chain. Further, there is a drawback that it is extremely difficult to physically remove the catalyst after the hydrogenation is completed, and the catalyst cannot be practically completely separated. Therefore, in order to economically hydrogenate the polymer, it is strongly desired to develop a highly active hydrogenation catalyst that exhibits activity at a use amount that does not require deashing, or a catalyst that can be deashed extremely easily. There is.

The present inventors have already combined a specific titanocene compound with an alkyllithium to hydrogenate an olefin compound (JP-A-61-33132, JP-A-1-53851), a metallocene compound and an organic compound. A method of hydrogenating an olefinically unsaturated (co) polymer by combining aluminum, zinc and magnesium (Japanese Patent Laid-Open No. SHO 6-61138).
JP-A No. 1-28507 and JP-A No. 62-209103), a method of hydrogenating a living polymer containing an olefinically unsaturated group with a combination of a specific titanocene compound and alkyl lithium (JP-A No. 61-47706). , JP-A-63-5402) and the like. But,
Although these methods are highly active, it is difficult to handle the hydrogenated catalyst, and long-term storage stability is also difficult.

On the other hand, a method of hydrogenating an olefinic double bond in a polymer containing an olefinically unsaturated double bond with a combination of a specific titanocene compound and alkoxylithium (JP-A-1-275605) is also disclosed. ing.
This method further requires an expensive organometallic compound other than alkoxylithium as a reducing agent. Further, a method of hydrogenating an olefinic double bond in a polymer containing an olefinic unsaturated double bond with a combination of a specific titanocene compound, an olefin compound and a reducing agent (JP-A-2-172537).
Japanese patent publication). Although this indicates storage stability and activity reproducibility as effects, it has a drawback that the long-term storage stability for one month or more is not sufficient. In order to solve these problems, the present inventors have applied for a method of hydrogenating an olefin compound with a combination of a liquid rubber having a specific microstructure, a specific titanocene, and a reducing agent (JP-A-4-96905). Issue). However, even with this method, long-term storage stability for several months was not sufficient, and further improvement was desired.

[0006]

The object of the present invention is to provide an ultra-high activity hydrogenation product which is stable and easy to handle, can withstand long-term storage for several months, and exhibits reproducible activity with an extremely small amount during the hydrogenation reaction. It is to provide a catalyst and to provide a method for producing a hydrogenated polymer having excellent weather resistance, oxidation resistance and ozone resistance using the catalyst.

[0007]

In order to solve the above problems, the first aspect of the present invention comprises the following components (A) to (D), wherein (A) is present in the presence of (C). A composite catalyst for hydrogenating an olefin compound, which comprises reducing (B) and then adding (D) to prepare the mixture.

(A) At least one of the titanocene compounds represented by the following general formula (1).

[Chemical 4] (However, R ¹ and R ² represent a group selected from a C _{1 to} C ₁₂ hydrocarbon group, an aryloxy group, an alkoxyl group, a halogen group, and a carbonyl group, and R ¹ and R ² are the same. Or they may be different. Cp represents a cyclopentadienyl group.)

(B) Li-containing, Na, which has a reducing ability,
At least one reducing agent selected from K, Mg, Ba, Zn, Al and Ca compounds. (C) An olefinic unsaturated double bond-containing polymer in which the ratio of the amount of side chain olefinic unsaturated double bonds to the total amount of olefinic unsaturated double bonds is 0.3 to 1. (D) Alcohol compound, ether compound, thioether compound, ketone compound, sulfoxide compound, carboxylic acid compound, carboxylic acid ester compound, aldehyde compound, lactone compound, amine compound, amide compound,
At least one polar compound selected from the group of nitrile compounds, epoxy compounds and oxime compounds.

The second aspect of the present invention comprises the following components (E) in addition to the components (A) to (D), wherein (A) is reduced with (B) in the presence of (C) and (E). A composite catalyst for hydrogenating an olefin compound, characterized in that (D) is added to the mixture and then prepared. (E) An alkaline compound represented by the following general formula (2). R ³ OM (2) (where M is at least one alkali metal atom selected from lithium, sodium and potassium. R ³ is C ₁
To C ₁₂ alkyl group, aryl group, aralkyl group or hydrocarbon group having oxygen atom and / or nitrogen atom. )

A third aspect of the present invention is composed of the following components (E) in addition to the components (A) to (D), and after reducing (A) with (B) in the presence of (C): (D) (E) is added and compounded, It is a composite catalyst for hydrogenating an olefin compound. (E) An alkaline compound represented by the following general formula (Formula 7). R ³ OM (2) (where M is at least one alkali metal atom selected from lithium, sodium and potassium. R ³ is C ₁
To C ₁₂ alkyl group, aryl group, aralkyl group or hydrocarbon group having oxygen atom and / or nitrogen atom. )

A fourth aspect of the present invention is to bring a conjugated diene-based polymer or a copolymer of a conjugated diene and a vinyl aromatic hydrocarbon into contact with hydrogen in an inert organic solvent to obtain the polymer.
When hydrogenating the olefinically unsaturated double bond, the composite catalyst according to claims 1 to 3 is prepared in advance in a catalyst tank and transferred to the hydrogenation tank to be used as the hydrogenation catalyst. A method for producing a hydrogenated conjugated diene-based polymer, which is characterized.

In a fifth aspect of the present invention, a conjugated diene polymer or a copolymer of a conjugated diene and a vinyl aromatic hydrocarbon is brought into contact with hydrogen in an inert organic solvent to obtain the polymer.
A method for producing a hydrogenated conjugated diene polymer, which comprises using the composite catalyst according to claim 2 or 3 as a catalyst for the hydrogenation when hydrogenating the olefinically unsaturated double bond. In the present invention, the conjugated diene-based polymer or the copolymer of the conjugated diene and the vinyl aromatic hydrocarbon is preferably a vinyl aromatic hydrocarbon in which the conjugated diene moiety is 1,3-butadiene and / or isoprene. Is styrene and / or α-methylstyrene.

At least one of the titanocene compounds represented by the general formula (1) according to the present invention (A) and the compound (B) having a reducing power, and a olefinically unsaturated double bond in a side chain in a specific ratio or more. A olefinic unsaturated double bond of a conjugated diene-based polymer or a copolymer of a conjugated diene and a vinyl aromatic hydrocarbon in combination with an olefinic unsaturated double bond-containing polymer (C) having A method for hydrogenating the above has been applied for by the present inventors (Japanese Patent Laid-Open No. 4-96905). The inventors of the present invention further improved the activity of the olefin hydrogenation catalyst of the earlier application, and further diligently studied a hydrogenation catalyst having excellent storage stability for several months. As a result, (C) a liquid olefin having a specific microstructure. (A) a titanocene compound having a specific structure in the presence of a polymer containing a polyunsaturated double bond, and (D) an alcohol
Group of phenol compounds, ether compounds, thioether compounds, ketone compounds, sulfoxide compounds, carboxylic acid compounds, carboxylic acid ester compounds, aldehyde compounds, lactone compounds, amine compounds, amide compounds, nitrile compounds, epoxy compounds and oxime compounds A hydrogenated composite catalyst prepared by adding at least one polar compound selected from the group consisting of a conjugated diene-based polymer or a copolymer of a conjugated diene and a vinyl aromatic hydrocarbon eliminates an olefinically unsaturated double bond. The present invention has been completed based on the finding that the amount of ash used is unnecessary and the hydrogen is selectively hydrogenated under mild conditions, and that the long-term activity stability of the catalyst is also excellent.

The hydrogenation catalyst component (A) according to the present invention is represented by the following general formula (1).

Embedded image (However, R ¹ and R ² represent a group selected from a C _{1 to} C ₁₂ hydrocarbon group, an aryloxy group, an alkoxyl group, a halogen group, and a carbonyl group, and R ¹ and R ² are the same. Or they may be different. Cp represents a cyclopentadienyl group.)

Examples of the C _{1 to} C ₁₂ hydrocarbon group of R ¹ and R ² include a substituent represented by the following general formula (3).

[Chemical 6] (However, R ⁶ to R ⁸ represent hydrogen or a C ₁ to C ₄ alkyl hydrocarbon group, one or more of R ₆ to R ₈ are hydrogen, and n = 0 or 1)

In the general formula (3), R⁶To R⁸All
Alkyl groups are probably hydrogenated due to steric hindrance.
There is a case where it is not preferable because the property is slightly poor. Also, Archi
Compounds in which the hydrocarbon radical is in the ortho position relative to the central metal
Although the product has high activity, it is difficult to synthesize,
Yes. Specific examples of the catalyst component (A) include bis (η^Five
-Cyclopentadienyl) titanium dimethyl, bis
(Η^Five-Cyclopentadienyl) titanium diethyl,
Screw (η^Five-Cyclopentadienyl) titaniumdi n-
Butyl, bis (η^Five-Cyclopentadienyl) titaniu
Muzi-sec-butyl, bis (η^Five-Cyclopentadie
Nyl) titanium dihexyl, bis (η^Five-Cyclopen
Tadienyl) titanium dioctyl, bis (η^Five-Siku
Lopentadienyl) titanium dimethoxide, bis (η
^Five-Cyclopentadienyl) titanium diethoxide,
Screw (η^Five-Cyclopentadienyl) titanium dipro
Poxide, bis (η^Five-Cyclopentadienyl) titani
Ummdibutoxide, bis (η^Five-Cyclopentadiene
Le) titanium diphenyl, bis (η^Five-Cyclopenta
Dienyl) titanium di-m-tolyl, bis (η^Five− Shi
Clopentadienyl) titanium di-p-tolyl, bis
(Η^Five-Cyclopentadienyl) titanium di-m, p
-Xylyl, bis (η^Five-Cyclopentadienyl) tita
Nium di-4-ethylphenyl, bis (η^Five-Cyclope
Ntadienyl) titanium di-4-hexylphenyl,
Screw (η^Five-Cyclopentadienyl) titanium diphe
Noxide, bis (η^Five-Cyclopentadienyl) titani
Ummdifluoride, bis (η^Five-Cyclopentadiene
Le) titanium dibromide, bis (η^Five-Cyclopen
Tadienyl) titanium diiodide, bis (η^Five− Shi
Clopentadienyl) titanium chloride methyl, bi
Space (η^Five-Cyclopentadienyl) titanium chloride
Doetokiside, screw (η^Five-Cyclopentadienyl)
Titanium chloride phenoxide, bis (η^Five-Siku
Lopentadienyl) titanium dibenzyl and the like.
It These may be used alone or in combination with each other.
You can Among these titanocene compounds, conjugated die
Polymers or conjugated dienes and vinyl aromatic hydrocarbons
For olefinically unsaturated double bonds in copolymers with
It has a high hydrogenation activity and a good unsaturated double bond under mild conditions.
As a preferable one which is preferably selectively hydrogenated, bis (η
^Five-Cyclopentadienyl) titanium dimethyl, bis
(Η^Five-Cyclopentadienyl) titanium di-n-bu
Chill, bis (η^Five-Cyclopentadienyl) titanium
Di-p-tolyl, bis (η^Five-Cyclopentadienyl)
Titanium dichloride, bis (η^Five-Cyclopentadi
(Enyl) titanium dicarbonyl, bis (η^Five-Cyclo
Pentadienyl) titanium diphenyl, bis (η^Five−
Cyclopentadienyl) titanium dibenzyl
Be done. Furthermore, it can be handled stably in the air, and the reducing property of (B)
When combined with a metal compound, it is the special
Preferred is bis (η^Five-Cyclopentadienyl)
Titanium dichloride, bis (η ^Five-Cyclopentadi
(Enyl) titanium di-p-tolyl, the latter being soluble in
It is most preferable because it also has excellent agent solubility.

On the other hand, as the catalyst component (B), an organometallic compound or a metal-containing compound capable of reducing the titanocene compound of the catalyst component (A) is used. These include organic lithium compounds, organic sodium compounds, organic potassium compounds, organic zinc compounds, organic barium compounds, organic magnesium compounds, organic aluminum compounds, etc., but they may be used alone or in combination with each other (A). The polymer can be hydrogenated.

Specific examples of the Li-containing compound include methyllithium, ethyllithium, n-propyllithium, isopropyllithium, n-butyllithium, sec-butyllithium, isobutyllithium, t-butyllithium, n-pentyllithium, n. -Hexyl lithium, phenyl lithium, cyclopentadienyl lithium, m-
Organolithium compounds such as tolyllithium, p-tolyllithium, xylyllithium, dimethylaminolithium, diethylaminolithium and the like can be mentioned. Further, an organosilicon lithium compound such as trimethylsilyllithium, diethylmethylsilyllithium, dimethylethylsilyllithium, triethylsilyllithium or triphenylsilyllithium may be used.

Specific examples of the Na-containing compound include methyl sodium, ethyl sodium, n-propyl sodium, isopropyl sodium, n-butyl sodium,
sec-butyl sodium, isobutyl sodium, t
Examples include organic sodium compounds such as -butyl sodium, n-pentyl sodium, n-hexyl sodium, phenyl sodium, cyclopentadienyl sodium, m-tolyl sodium, p-tolyl sodium, xylyl sodium, and sodium naphthalene.

Specific examples of the K-containing compound include methyl potassium, ethyl potassium, n-propyl potassium, isopropyl potassium, n-butyl potassium, sec-butyl potassium, isobutyl potassium, t-butyl potassium,
Organic potassium compounds such as n-pentyl potassium, n-hexyl potassium, triphenylmethyl potassium, phenyl potassium, phenylethyl potassium, cyclopentadienyl potassium, m-tolyl potassium, p-tolyl potassium, xylyl potassium and potassium naphthalene Can be mentioned.

Examples of the Zn-containing compound include diethyl zinc, bis (η ⁵ -cyclopentadienyl) zinc, diphenyl zinc and the like. Further, examples of the Mg-containing compound include dimethyl magnesium, diethyl magnesium, dibutyl magnesium and ethyl butyl magnesium. , Methylmagnesium bromide, ethylmagnesium chloride, ethylmagnesium bromide, ethylmagnesium chloride, phenylmagnesium bromide, phenylmagnesium chloride, t-butylmagnesium chloride, t-butylmagnesium bromide and the like.

Further, as the Al-containing compound, trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, triphenyl aluminum, diethyl aluminum chloride, dimethyl aluminum chloride, ethyl aluminum dichloride, methyl aluminum sesquichloride, ethyl aluminum sesquichloride, diethyl aluminum hydride, Examples thereof include organic aluminum compounds such as diisobutylaluminum hydride, triphenylaluminum, tri (2-ethylhexyl) aluminum, (2-ethylhexyl) aluminum dichloride, methylaluminoxane and ethylaluminoxane.

Further, Ca-containing compounds include dialkyl calcium, diphenyl calcium and diaryl calcium compounds, and organic barium compounds include dialkyl barium, diphenyl barium and diaryl barium. In addition to these, lithium hydride, potassium hydride, sodium hydride,
Alkali (earth) metal hydrides such as calcium hydride, lithium aluminum hydride, sodium aluminum hydride, potassium aluminum hydride, diisobutyl sodium aluminum hydride, tri (t-butoxy) aluminum hydride, triethyl sodium aluminum hydride, diisobutyl sodium aluminum hydride, Triethyl sodium aluminum hydride,
A hydride containing two or more metals such as triethoxy sodium aluminum hydride and triethyl lithium aluminum hydride may be used.

The above catalyst components (B) which are reducing agents may be used as a mixture of two or more kinds, or may be a complex (art complex) of two or more kinds. Among these art complexes, complexes represented by the following general formulas (4) and (5) are also included. M ¹ (AlR ⁴ R ⁵ R ⁶ R ⁷ ) ... (4) M ¹ (MgR ⁴ R ⁵ R ⁶ ) ... (5) (wherein M ¹ is a lithium atom, a sodium atom and a potassium atom) At least one alkali metal atom selected from R ⁴ , R ⁴ is an alkyl group, aryl group or aralkyl group, R ⁵ is an alkyl group, aryl group, aralkyl group or halogen atom, R ⁶ is a halogen atom, R ⁷ Represents an alkyl group, an aryl group, an aralkyl group, an alkoxy group or an aryloxy group), and is at least one selected from the complex compounds represented by these.

The olefinic unsaturated double bond-containing weight whose ratio to the total amount of olefinic unsaturated double bonds in the side chain of the catalyst component (C) is 0.3 to 1 Examples of monomers used to make the coalesces include conjugated dienes, typically conjugated dienes having from 4 to about 12 hydrocarbons. Specific examples include 1,3-butadiene, isoprene, 2,3-dimethylbutadiene, 1,3-pentadiene, 2-methyl-
1,3-pentadiene, 1,3-hexadiene, 4,5
-Diethyl-1,3-octadiene, 3-butyl-1,
3-octadiene, etc. are mentioned. These may be used alone or in combination of two or more. 1,3-Butadiene and isoprene, which can be industrially advantageously developed and are relatively easy to handle, are particularly preferable, and polybutadiene, polyisoprene, and butadiene / isoprene copolymer are preferable.

Further, norbornadiene, cyclopentadiene, 2,3-dihydrodicyclopentadiene, and alkyl-substituted products thereof may be used alone or as a copolymer. The polymer of the catalyst component (C) has a number average molecular weight of 50.
It may be 0 or more and 1,000,000 or less. If the number average molecular weight is less than 500, the stabilizing effect is small, so a liquid rubber having a number average molecular weight of 500 or more that is easy to handle is desirable.

The liquid rubber is preferably liquid at room temperature, and usually has a number average molecular weight in the range of 500 to 10,000. When the number average molecular weight is 10,000 or more, there is no particular problem in terms of performance except that handling as a liquid becomes difficult. The microstructure is important in the polymer of the catalyst component (C). That is, "the ratio of the olefinically unsaturated double bond of the side chain to the total olefinic unsaturated double bond" is X, and "the olefinically unsaturated carbon-carbon double bond in the side chain of the component (C) polymer is used. The number of bonds is Y,
When "the total number of olefinically unsaturated carbon-carbon double bonds in the component (C) polymer" is Z, "the fraction of the olefinically unsaturated double bonds in the side chain to the total olefinic unsaturated double bonds" Is defined by X = Y / Z.

It is essential that this value is from 0.3 to 1, but within this range, the terminal may have a functional group such as a hydroxyl group, a carboxyl group, an amino group or an epoxy group. To give a specific example, in the case of polybutadiene, all olefinically unsaturated double bonds (cis 1,4 bond, trans 1,
It is sufficient that the olefinically unsaturated double bond (1,2 bond) in the side chain is in the range of 0.3 to 1 with respect to 4 bonds, 1,2 bond). Becomes unstable and difficult to handle, storage stability is poor, and if not handled properly, reproducibility also becomes a problem.

Further, this polymer may be a copolymer with a conjugated diene / aromatic vinyl compound. Specific examples of the aromatic vinyl compound include styrene, t-butylstyrene,
Examples thereof include α-methylstyrene, p-methylstyrene, divinylbenzene, 1,1-diphenylethylene, N, N-diethyl-p-aminoethylstyrene and the like, and styrene is particularly preferable. As a concrete example of the copolymer, a butadiene / styrene copolymer, an isoprene / styrene copolymer and the like are most suitable. These copolymers may be random, block, star block, taper block, etc. and are not particularly limited.

The amount of the bound aromatic vinyl compound is preferably 70% or less. If this amount exceeds 70%, the ratio of the olefinically unsaturated double bond amount of the side chain of the conjugated diene portion to the total amount of the copolymer is substantially reduced, and the stabilizing effect of the catalyst is reduced. Since a large amount of the catalyst component (C) is required, the physical properties of the hydrogenated conjugated diene polymer and the copolymer of the conjugated diene and the vinyl aromatic hydrocarbon may change, which is not preferable in some cases. is there.

Most importantly, it is necessary that the ratio of the amount of olefinically unsaturated double bonds in the side chain of the conjugated diene part of the component (C) to the total olefinic double bonds is 0.3 to 1. The preferable fraction is 0.5 to 0.99.
These catalyst components (C) may be polymerized by any known method such as radical polymerization, cationic polymerization, anionic polymerization and coordinated anionic polymerization, but the amount of olefinically unsaturated double bond in the side chain is increased. In the presence of a polar solvent or in the presence of organic lithium or organic sodium compound as a catalyst, it is obtained by living anionic polymerization, or by coordination anionic polymerization with a cobalt-based Ziegler type catalyst, or ethylene and dicyclohexene are used. It is preferably obtained by copolymerizing pentadienes.

Specific examples of the polar solvent include tetrahydrofuran, tetramethylethylenediamine, trimethylamine, triethylamine, ethyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether,
Examples include dipiperidinoethane. Examples of the Li-based catalyst include methyllithium, ethyllithium, n-propyllithium, isopropyllithium, n-butyllium, s.
ec-butyllithium, isobutyllithium, tert
-Butyllithium, n-pentyllithium, n-hexyllithium, trimethylsilyllithium, and the like. Examples of the Na-based catalyst include methyl sodium, ethyl sodium, n-propyl sodium, isopropyl sodium, n-butyl sodium, sec-butyl sodium, isobutyl sodium, phenyl sodium, sodium naphthalene, and cyclopentadienyl sodium.

The catalyst component (D) is an alcohol compound, ether compound, thioether compound, ketone compound, sulfoxide compound, carboxylic acid compound, carboxylic acid ester compound, aldehyde compound, lactone compound, amine compound, amide. At least 1 selected from the group of compounds, nitrile compounds, epoxy compounds and oxime compounds
Is a polar compound of the species.

Of these, specific examples of the alcohol compound include methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, sec-butyl alcohol.
, Tert-butyl alcohol, n-amyl alcohol
, Isoamyl alcohol, hexyl alcohol and its isomers, heptyl alcohol and its isomers, octyl alcohol and its isomers, capryl alcohol, nonyl alcohol and its isomers, decyl alcohol And isomers thereof, benzyl alcohol, phenol, cresol, monovalent alcohol such as 2,6-di-tert-butyl-p-cresol, ethylene glycol, propylene glycol , Butanediol, pentylglycol, neopentylglycol, hexylglycol, heptylglycol and glycol (divalent alcohol) which is an isomer of these glycols. . Further, it may be a compound having another functional group in one molecule, such as a trivalent alcohol such as glycerin, ethanolamine, glycidyl alcohol or the like.

As specific examples of ether compounds,
Dimethyl ether, diethyl ether, di-n-propyl ether, diisopropyl ether, di-n-butyl ether, di-sec-butyl ether, diphenyl ether, methyl ethyl ether, ethyl butyl ether, Butyl vinyl ether, anisole, ethyl phenyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol
Examples thereof include rudibutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, furan, tetrahydrofuran, α-methoxytetrahydrofuran, pyran, tetrahydropyran and dioxane. Further, a compound having another functional group in one molecule such as tetrahydrofuran carboxylic acid may be used.

Specific examples of the thioether compound include dimethyl sulfide, diethyl sulfide and di-n.
-Butyl sulfide, di-sec-butyl sulfide,
Di-t-butyl sulfide, diphenyl sulfide, methyl ethyl sulfide, ethyl butyl sulfide, thioanisole, ethyl phenyl sulfide, thiophene,
Tetrahydrothiophene etc. are mentioned.

Further, specific examples of the ketone compound include acetone, diethyl ketone, di-n-propyl ketone, diisopropyl ketone, di-n-butyl ketone and di-se.
Examples thereof include c-butyl ketone, di-t-butyl ketone, benzophenone, methyl ethyl ketone, acetophenone, benzyl phenyl ketone, propiophenone, cyclopentanone, cyclohexanone, diacetyl, acetylacetone and benzoylacetone.

Further, specific examples of the sulfoxide compound include dimethyl sulfoxide, diethyl sulfoxide, tetramethylene sulfoxide, pentamethylene sulfoxide, diphenyl sulfoxide, dibenzyl sulfoxide, p-tolyl sulfoxide and the like.

Specific examples of the carboxylic acid compound include formic acid, acetic acid, propionic acid, butyric acid, caproic acid, lauric acid, palmitic acid, stearic acid, cyclohexylpropionic acid, cyclohexylcaproic acid, benzoic acid, phenylacetic acid, o- Toluic acid, m-toluic acid,
Monobasic acids such as p-toluic acid, acrylic acid, methacrylic acid, oxalic acid, maleic acid, malonic acid, fumaric acid, succinic acid,
Dibasic acids such as adipic acid, pimelic acid, suberic acid, sebacic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, naphthalic acid, diphenic acid, trimellitic acid, pyromellitic acid and their derivatives Examples include polybasic acids. Further, it may be a compound having another functional group in one molecule, such as hydroxybenzoic acid.

Further, specific examples of the carboxylic acid ester include formic acid, acetic acid, propionic acid, butyric acid, caproic acid, lauric acid, palmitic acid, stearic acid, cyclohexylpropionic acid, cyclohexylcaproic acid, benzoic acid, phenylacetic acid, o-. Toluic acid, m-toluic acid,
Monobasic acids such as p-toluic acid, acrylic acid, methacrylic acid, oxalic acid, maleic acid, malonic acid, fumaric acid, succinic acid,
Dibasic acids such as adipic acid, pimelic acid, suberic acid, sebacic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, naphthalic acid, diphenic acid and methyl alcohol
, N-propyl alcohol, isopropyl alcohol
, N-butyl alcohol, sec-butyl alcohol
, T-butyl alcohol, amyl alcohol, hexyl alcohol, heptyl alcohol, isoheptyl alcohol, sec-heptyl alcohol, octyl alcohol and its isomers, phenol and cresol. And esters with alcohols such as glycidyl alcohol and β-ketoesters such as methyl acetoacetate and ethyl acetoacetate.

Further, specific examples of the lactone compound include:
Examples include β-propiolactone, δ-valerolactone, ε-caprolactone, and lactone compounds corresponding to the following acids. That is, as this acid, 2-methyl-3
-Hydroxy-propionic acid, 3-hydroxynonanone or 3-hydroxypelargonic acid, 2-dodecyl-3
-Hydroxypropionic acid, 2-cyclopentyl-3-
Hydroxypropionic acid, 3-phenyl-3-hydroxypropionic acid, 2-naphthyl-3-hydroxypropionic acid, 2-n-butyl-3-cyclohexyl-3-hydroxypropionic acid, 2-phenyl-3-hydroxytridecanoic acid , 2- (2-ethylcyclopentyl) -3
-Hydroxypropionic acid, 2-methylphenyl-3-
Hydroxypropionic acid, 3-benzyl-3-hydroxypropionic acid, 2,2-dimethyl-3-hydroxypropionic acid, 2-methyl-5-hydroxyvaleric acid,
3-cyclohexyl-5-hydroxyvaleric acid, 4-
Phenyl-5-hydroxyvaleric acid, 2-heptyl-
4-Cyclopentyl-5-hydroxyvaleric acid, 2-
Methyl-3-phenyl-5-hydroxyvaleric acid, 3
-(2-Cyclohexylethyl) -5-hydroxyvaleric acid, 2- (2-phenylethyl) -4- (4-cyclohexylbenzyl) -5-hydroxyvaleric acid, benzyl-5-hydroxyvaleric acid, 3 -Ethyl-5
Isopropyl-6-hydroxycaproic acid, 2-cyclopentyl-4-hexyl-6-hydroxycaproic acid,
2-iclopentyl-4-hexyl-6-hydroxycaproic acid, 3-phenyl-6-hydroxycaproic acid,
3- (3,5-diethyl-cyclohexyl) -5-ethyl-6-hydroxycaproic acid, 4- (3-phenyl-
Propyl) -6-hydroxycaproic acid, 2-benzyl-5-isobutyl-6-hydroxycaproic acid, 7-phenyl-6-hydroxyl-octenoic acid, 2,2-di (1-cyclohexenyl) -5-hydroxy- 5-heptenoic acid, 2,2-dipropenyl-5-hydroxy-5-
Heptenoic acid, 2,2-dimethyl-4-propenyl-3-
Hydroxy-3,5-heptadienoic acid and the like can be mentioned.

Further, specific examples of amine compounds include isopropylamine, n-butylamine, sec-butylamine, t-butylamine, n-amylamine, t-amylamine, n-hexylamine, n-heptylamine, aniline, benzylamine, o-anisidine, m-
Anisidine, p-anisidine, α-naphthylamine, dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, di-sec-butylamine, di-t-butylamine, di-
n-amylamine, diisoamylamine, dibenzylamine, N-methylaniline, N-ethylaniline, N-
Ethyl-o-toluidine, N-ethyl-m-toluidine, N-ethyl-p-toluidine, triethylamine,
Tri-n-propylamine, tri-n-butylamine,
Tri-n-amylamine, triisoamylamine, tri-n-hexylamine, tribenzylamine, triphenylmethylamine, N, N-dimethylbenzylamine,
N, N-dimethylaniline, N, N-diethylaniline, N, N-diethyl-o-toluidine, N, N-diethyl-m-toluidine, N, N-diethyl-p-toluidine, N, N-dimethyl- α-naphthylamine, N,
Examples thereof include N, N ′, N′-tetramethylethylenediamine, pyrrolidine, piperidine, N-methylpyrrolidine, N-methylpiperidine, pyridine, piperazine, 2-acetylpyridine, N-benzylpiperazine, quinoline and morpholine.

Further, the amide compound has at least one -C (= O) -N <or -C (= S) -N <in the molecule.
A compound having a bond, specifically, N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, acetamide, propionamide, benzamide, acetanilide, benzanilide, N-methylacetanilide, N, N- Dimethylthioformamide, N, N-dimethyl-N, N '-(p-dimethylamino) benzamide, N-ethylene-N-methyl-8-quinolinecarboxamide, N, N'-dimethylnicotinamide, N, N- Dimethylmethacrylamide, N-methylphthalimide, N-phenylphthalimide, N-acetyl-ε-caprolactam, N, N, N ′, N′-tetramethylphthalamide, 10-acetylphenoxazine, 3,7-bis (dimethyl) Amino) -10-benzoylphenothiazine, 10-a Chill phenothiazines,
In addition to 3,7-bis (dimethylamino) -10-benzoylphenothiazine, N-ethyl-N-methyl-8-quinolinecarboxamide, N, N′-dimethylurea,
N, N'-diethylurea, N, N'-dimethylethyleneurea, N, N, N ', N'-tetramethylurea, N, N
Examples include linear urea compounds such as -dimethyl-N ', N'-diethylurea and N, N-dimethyl-N', N'-diphenylurea.

Further, specific examples of the nitrile compound include:
Acetonitrile, propionitrile, benzonitrile,
Benzyl nitrile, adiponitrile, malononitrile,
N, N-dimethylamino-benzyl nitrile etc. are mentioned.

Further, specific examples of the epoxy compound include:
1,3-butadiene monooxide, 1,3-butadiene oxide, 1,2-butylene oxide, 2,3-butylene oxide, cyclohexene oxide, 1,2-epoxycyclododecane, 1,2-epoxydecane, 1,2 −
Epoxy eicosane, 1,2-epoxy heptane, 1,
2-epoxyhexadecane, 1,2-epoxyoctadecane, 1,2-epoxyoctane, ethylene glycol diglycidyl ether, 1,2-epoxytetradecane, hexamethylene oxide, isobutylene oxide,
1,7-octadiene epoxide, 2-phenylpropylene oxide, propylene oxide, trans-stilbene oxide, styrene oxide, epoxidized 1,2-
Examples thereof include polybutadiene, epoxidized linseed oil, glycidyl methyl ether, glycidyl n-butyl ether, glycidyl allyl ether, glycidyl methacrylate and glycidyl acrylate.

Further, specific examples of the oxime compound include
Acetoxime, methyl ethyl ketone oxime, diethyl ketone oxime, acetophenone oxime, benzophenone oxime, benzyl phenyl ketone oxime, cyclopentanone oxime, cyclohexanone oxime,
Examples thereof include benzaldehyde oxime.

The present invention also contains, as the component (E), an alkali compound represented by the following general formula (2) in addition to the components (A) to (D), and the presence of (C) and (E). Below, (A)
Is reduced with (B), and then (D) is added to the mixture, and the compounded catalyst for hydrogenating an olefin compound is prepared, and in addition to the components (A) to (D), the following general formula (2) ) Contains an alkaline compound represented by the formula (E) as a component,
(A) is reduced with (B) in the presence of
A composite catalyst for hydrogenating an olefin compound, which is characterized in that (E) is added and prepared, is also included. R ³ OM (2) (where M is at least one alkali metal atom selected from lithium, sodium and potassium. R ³ is C ₁
Alkyl -C _12, ant - represents a group, a hydrocarbon group having an aralkyl group or an oxygen atom and / or nitrogen atoms. )

Specific examples of the component (E) include methoxylithium, ethoxylithium, n-propoxylithium, 1-propoxylithium, n-butoxylithium, sec-butoxylithium, t-butoxylithium, pentyloxylithium and hexyl. Oxylithium, heptyloxylithium, octyloxylithium, phenoxylithium, 4-methylphenoxylithium, 4-methylbenzyloxylithium, 2,6-di-
t-butyl-4-methylphenoxylithium, benzyloxylithium, (2-butoxyethoxy) lithium,
[2- (N, N-Dimethylamino) ethoxy] lithium, methoxysodium, ethoxysodium, methoxypotassium, and further a phenol or a phenol-based stabilizer is reacted with alkyllithium, alkylsodium, alkylpotassium. Obtained lithium phenol
Also used are sodium, sodium phenolate and potassium phenolate compounds. Specific examples of such a phenolic stabilizer include 1-oxy-3-methyl-4-isopropylbenzene, 2,6-di-t-butylphenol, 2,6-
Di-t-butyl-4-ethylphenol, 2,6-di-
t-butyl-p-cresol, 2,6-di-t-butyl-4-n-butylphenol, 4-hydroxymethyl-
2,6-di-t-butylphenol, butylhydroxyanisole, 2- (1-methylcyclohexyl) -4,
6-dimethylphenol, 2,4-dimethyl-6-t-
Butylphenol, 2-methyl-4,6-dinonylphenol, 2,6-di-t-butyl-α-dimethylamino-p-cresol, methylene-bis- (dimethyl-4,
6-phenol), 2,2'-methylene-bis- (4-
Methyl-6-t-butylphenol), 2,2'-methylene-bis- (4-methyl-6-cyclohexylphenol), 2,2'-methylene-bis- (4-ethyl-6)
-T-butylphenol), 4,4'-methylene-bis- (2,6-di-t-butylphenol), 2,2'-
Methylene-bis- (6-α-methyl-benzyl-p-cresol) and the like can be mentioned.

The most versatile stabilizer is 2,6-di-t.
Particularly preferred is 2,6-di-t-butyl-4-methylphenoxylithium in which the hydroxyl group of -butyl-p-cresol is -OLi. As the component (E), an alkali compound produced by previously reacting an alkali metal or organic alkali metal compound with an alcohol compound, a ketone compound, a phenol or a derivative thereof, or a living polymer may be used. The alkali compound formed when the terminal of the compound is terminated with an alcohol compound, a ketone compound, a phenol or its derivative or the like may be used as it is.

The composite hydrogenation catalyst of the present invention can be applied to all compounds having an olefinically unsaturated double bond. For example, ethylene, propylene, butene, pentene,
Aliphatic olefins such as hexene, heptene, octene and their isomers, cyclopentene, methylcyclopentene, cyclopentadiene, cyclohexene, cycloaliphatic olefins such as methylcyclohexene, cyclohexadiene, monomers such as styrene, butadiene and isoprene, It can also be applied to unsaturated fatty acids and their derivatives, unsaturated liquid oligomers, low molecular weight polymers containing at least one olefinically unsaturated double bond in the molecule, and the like.

Further, the present invention can be applied to selective hydrogenation of olefinically unsaturated double bonds of a conjugated diene copolymer or a copolymer of a conjugated diene and an olefin monomer. The selective hydrogenation here is to selectively hydrogenate the conjugated diene copolymer, the olefinically unsaturated double bond of the conjugated diene portion of the conjugated diene and the copolymer of the olefin monomer, and the olefin. When a vinyl aromatic compound is used as the monomer, it means that the carbon-carbon double bond of the aromatic ring is not substantially hydrogenated. The selective hydrogenated product of an olefinic unsaturated double bond of a conjugated diene copolymer or a copolymer of a conjugated diene and an olefin monomer is industrially useful as an elastic body or a thermoplastic elastic body.

The conjugated diene used for producing such a conjugated diene polymer generally includes a conjugated diene having 4 to about 12 carbon atoms, and specific examples thereof include 1,3-butadiene. , Isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 2-
Methyl-1,3-pentadiene, 1,3-hexadiene, 4,5-diethyl-1,3-octadiene, 3-butyl-1,3-octadiene and the like can be mentioned. From the standpoint of obtaining an elastic body that can be industrially developed and has excellent physical properties,
1,3-butadiene and isoprene are preferred.

The microstructure of the butadiene part includes 1,2
Although there are bonds and 1,4 bonds (cis + trans), both of the catalysts of the present invention can quantitatively hydrogenate. Further, in the isoprene portion, there are olefinic unsaturated bonds in the side chains of 1,2 bonds, 3,4 bonds and the main chain of 1,4 bonds (cis + trans), and each has the following general formula (6) , (7), (8).

[0055]

[Chemical 7]

[0056]

Embedded image

[0057]

[Chemical 9]

These structures and hydrogenation rates are ¹ H-NM
It can be measured by R. Using the method of the present invention, the side chains of the 1,2 bond, 1,4 bond of the butadiene moiety and the 1,2 bond (6), 3,4 bond (7) of the isoprene moiety are particularly selectively hydrogenated. Is possible.

When 1,3-butadiene is selected as the main component of the conjugated diene polymer to be hydrogenated in the present invention, in order to develop the elastomer elasticity especially at low temperature to room temperature, the microstructure of the butadiene unit part is used. The amount of 1,2 bonds is 8% or more, preferably 20% or more, and a particularly preferable range is 30 to 80%. When isoprene is selected as the main component of the conjugated diene polymer, the amount of 1,4 bonds as the microstructure of the isoprene unit is 50% or more, more preferably 75% or more for the same reason. .

As the olefin monomer copolymerizable with at least one conjugated diene, vinyl-substituted aromatic hydrocarbon is particularly preferable. That is, in order to sufficiently exert the effect of the present invention of selectively hydrogenating only unsaturated double bonds of conjugated diene units, and obtain an industrially useful and valuable elastic body or thermoplastic elastic body, Copolymers of dienes and vinyl-substituted aromatic hydrocarbons are of particular interest. Specific examples of the vinyl aromatic hydrocarbon used include styrene and ter
t-butylstyrene, α-methylstyrene, p-methylstyrene, divinylbenzene, 1,1-diphenylethylene, N, N-dimethyl-p-aminoethylstyrene,
Examples thereof include N, N-diethyl-p-aminoethylstyrene, and styrene and / or α-methylstyrene are particularly preferable. Specific examples of copolymers include butadiene / styrene copolymer, isoprene / styrene copolymer,
Butadiene / isoprene / styrene copolymer and the like are most suitable because they give hydrogenated copolymers of high industrial value.
These may be random, block or tapered block copolymers.

In such a copolymer, the block copolymer provides the most industrially useful hydrogenated polymer as a thermoplastic elastic body, but the block having at least one conjugated diene-based block at the end is used. The copolymer is particularly preferably used because it gives a hydrogenated polymer which is excellent in processability, compatibility with other olefin polymers, adhesiveness and the like as compared with a copolymer having no conjugated diene block at the terminal. Under the catalyst of the present invention and the preferred hydrogenation conditions, hydrogenation of carbon-carbon double bonds (aromatic rings) of vinyl-substituted aromatic hydrocarbon units in such copolymers does not substantially occur.

A preferred embodiment of the hydrogenation reaction of the present invention is
It is carried out in the state of a solution in which a compound having an olefinically unsaturated double bond or the polymer is dissolved in an inert organic solvent. By "inert organic solvent" herein is meant a solvent that does not react with any of the participants in the hydrogenation reaction. Suitable solvents are, for example, aliphatic hydrocarbons such as n-pentane, n-hexane, n-heptane and n-octane, alicyclic hydrocarbons such as cyclohexane, cycloheptane and cycloheptane, diethyl ether, It is a single or mixture of ethers such as tetrahydrofuran. Also, aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene can be used only if the aromatic double bonds are not hydrogenated under the selected hydrogenation conditions.

In the hydrogenation reaction of the present invention, generally, the solution to be hydrogenated is maintained at a predetermined temperature in hydrogen or an inert atmosphere, and a hydrogenation catalyst is added with or without stirring. Then, it is carried out by introducing hydrogen gas and pressurizing it to a predetermined pressure. The inert atmosphere means, for example, an atmosphere that does not react with any participant in the hydrogenation reaction such as helium, neon, or argon. Air and oxygen are not preferable because they oxidize the catalyst components and deactivate the catalyst. Further, nitrogen may act as a catalyst poison during the hydrogenation reaction and reduce the hydrogenation activity. In particular, it is most preferable that the hydrogenation reactor has an atmosphere of hydrogen gas alone.

The composite hydrogenated catalyst of the first aspect of the present invention is obtained by reducing the catalyst component (A) with the catalyst component (B) in the presence of the catalyst component (C) in a suitable solvent in a catalyst tank. , The catalyst component (D) is added last. (A)
The order of adding (B) and (C) may be arbitrary, but (D) must be the last. The second aspect of the present invention
In the case of coexisting with the component (E), which is the invention of claim 1, the catalyst component (A) is reduced with the catalyst component (B) in the presence of the catalyst components (C) and (E), and then the catalyst component (D) is finally added. Or by reducing the catalyst component (A) with the catalyst component (B) in the presence of the catalyst component (C), and finally adding the catalyst components (D) and (E). In this case, the order of adding (A), (B), (C), and (E) may be arbitrary, but (D) must be the last.

When the conjugated diene polymer to be hydrogenated or the copolymer of the conjugated diene and the vinyl aromatic hydrocarbon is obtained by living anionic polymerization, it is usually the same as the active end when stopping the active end. The deactivating agent is added in an amount of not more than a molar amount or in excess, but when an excessive alcohol or ketone compound is used as the deactivating agent, an alkoxy alkali metal [component (E) of the present invention] and a polar compound are added to the system. [Component (D) of the present invention] may be present. In this case, (A), (B), (C), (D) and (E) catalyst components are present in the hydrogenation reaction system, and (A), (B) and (C) prepared in advance in the catalyst tank. It is indistinguishable from the appearance when the catalyst component was added to the hydrogenation reaction system.

However, even if the component (E) is present in the hydrogenation tank in advance, (A) is replaced with (B) under the coexistence of (C) [or (C) (E)] as in the present invention. Give back,
Finally, a hydrogenated catalyst prepared by mixing a mixture containing (D) in a catalyst tank has far superior long-term storage stability. The reason for this is not clear, but it is presumed that the life of the catalytically active species differs depending on the preparation method of the catalyst.

The compounding atmosphere of the composite hydrogenation catalyst of the present invention may be hydrogen in addition to the above-mentioned inert atmosphere. The reduction temperature and the storage temperature are -50 ° C to 50 ° C, and -20 ° C to
30 ° C. is particularly preferred. The time required for the reduction varies depending on the reduction temperature, but at 25 ° C., it is several seconds to 60 days, preferably 1 minute to 20 days. The catalyst component (B) needs to be handled under the above-mentioned inert atmosphere. The catalyst component (A) may be stable in the air, but it is preferably handled in an inert atmosphere.

It is preferable that the catalyst components (A), (B), (C) and (D) constituting the composite hydrogenation catalyst of the present invention are used as a solution of the above-mentioned inert organic solvent because they are easy to handle. As the inert organic solvent used when used as a solution, the above-mentioned various solvents that do not react with any of the participants in the hydrogenation reaction can be used. It is preferably the same solvent as that used for the hydrogenation reaction.

When the composite hydrogenation catalyst is added to the hydrogenation reactor (hydrogenation tank), it is most preferable to carry out it under a hydrogen atmosphere. The temperature at the time of adding is -30 ° C to 100 ° C,
It is preferable to add at a temperature of −10 ° C. to 50 ° C. immediately before the hydrogenation reaction. The mixing ratio of each catalyst component for exhibiting high hydrogenation activity and hydrogenation selectivity is the ratio of the number of moles of the metal of the catalyst component (B) to the number of moles of the catalyst component (A) (hereinafter Metal (B)). / Metal (A) molar ratio) is about 20 or less. MetaL (B) / M
If the molar ratio of etal (A) is more than 20, not only is it uneconomical to use an excessive amount of expensive catalyst component (B) that does not contribute to substantial activity improvement, but also undesired side reactions are likely to occur. Metal (B) / Metal
(A) It has hydrogenation activity in the molar ratio range of 0.05 to 20. More preferably, it is in the range of 0.05 to 5, and the hydrogenation activity is remarkably improved.

When the substance to be hydrogenated in the hydrogenation tank is a living polymer obtained by living anionic polymerization, the living end acts as a reducing agent, so that the polymer having a living active end is hydrogenated. In order for this optimal Meta
In order to achieve the 1 (B) / Metal (A) molar ratio, it is preferable to deactivate the compound with various active hydrogen or halogen. Examples of such compounds having active hydrogen include water and methanol, ethanol, n-propanol, n-butanol, sec-butanol, t-butanol, 1-pentanol, 2-pentanol, 3- Pentanol, 1-hexanol, 2-hexanol, 3
-Hexanol, 1-heptanol, 2-heptanol
, 3-heptanol, 4-heptanol, octano
, Nonanol, decanol, undecanol, lauryl alcohol, allyl alcohol, cyclohexanol
, Cyclopentanol, benzyl alcohol and other alcohols, phenol, o-cresol, m-cresol
, P-cresol, p-allylphenol, 2,6-
Examples thereof include phenols such as di-t-butyl-p-cresol, xylenol, dihydroanthraquinone, dihydroxycoumarin, 1-hydroxyanthraquinone, m-hydroxybenzyl alcohol, resorcinol and leucoaurine.

As the acid, acetic acid, propionic acid, butyric acid, isoacetic acid, pentanoic acid, hexanoic acid, heptanoic acid,
Decalic acid, myristic acid, stearic acid, behenic acid,
Examples thereof include organic carboxylic acids such as benzoic acid. Benzyl chloride as a compound having halogen,
Examples thereof include trimethylsilyl chloride (bromide), t-butylsilyl chloride (bromide), methyl chloride (bromide), ethyl chloride (bromide), propyl chloride (bromide), n-butyl chloride (bromide), and the like. These may be used alone or in combination of two or more.

The addition amount of the catalyst component (C) is preferably 10 to 500 by weight ratio with respect to the catalyst of the catalyst component (A). If it is less than 10, the effect of stabilizing the storage and reducing the amount of catalyst becomes small. Even if this ratio exceeds 500, the hydrogenation activity is good, but when the substance to be hydrogenated is a polymer, it may be difficult to separate the hydrogenated polymer from the catalyst component (C), and therefore, depending on the case. Affects physical properties.

The substance to be hydrogenated is an olefinically unsaturated double bond-containing polymer, and the content of olefinically unsaturated double bonds in the side chain is 0.3 with respect to the total olefinic unsaturated double bonds. In the case of 1 to 1, a part thereof may be transferred to the catalyst tank and used as the catalyst component (C), or may be used as a mixture with another catalyst component (C). When the molar ratio of the catalyst component (D) to the catalyst of the catalyst component (B) is (D) / (B), the hydrogenation activity is high and the storage stability is high. -The hydrogenation activity will be extremely long-lasting.

When the catalyst component (E) is used, the addition amount thereof is (E) / (A) in a molar ratio of 3 to the catalyst component (A).
The range of 0 or less, preferably 20 or less, and more preferably 10 or less is desirable. Even if this ratio exceeds 30, it retains the catalytic activity of hydrogenation, but it uses a large amount of component (E) that does not substantially contribute to the activity improvement, which is not only uneconomical, but also polymer. It is not preferable because it may cause a side reaction such as gelation. When the substance to be hydrogenated in the hydrogenation tank is a living polymer obtained by living anionic polymerization, these components (E) are deactivated with a derivative such as alcohol or phenol at the living active terminal. Alkali compounds generated when the reaction is carried out may be used, and a separate alcohol,
An alkali compound synthesized by reacting phenol with an alkali metal or an alkyl alkali compound may be used.

The amount of the catalyst added was 0.
002-20 mmol is sufficient. Within this addition amount range, it is possible to preferentially hydrogenate the olefinically unsaturated double bond of the hydrogenated substance, and the hydrogenation of the aromatic double bond in the copolymer does not substantially occur. Therefore, extremely high hydrogenation selectivity is realized. The hydrogenation reaction is possible even if the amount of addition exceeds 20 millimoles, but use of an excessive amount of catalyst becomes uneconomical and disadvantageous in that catalyst deashing and removal after the hydrogenation reaction become complicated. Further, the preferable amount of the catalyst to quantitatively hydrogenate the unsaturated double bond of the conjugated diene unit of the polymer under the selected conditions is 0.01 to 5 mmol per 100 g of the polymer.

The hydrogenation reaction of the present invention is carried out using elemental hydrogen, and more preferably, it is introduced into the substance to be hydrogenated in the form of gas. The hydrogenation reaction is more preferably carried out under stirring,
The introduced hydrogen can be brought into contact with the substance to be hydrogenated sufficiently quickly. The hydrogenation reaction is generally carried out in the temperature range of 0 to 150 ° C. If the temperature is lower than 0 ° C, the activity of the catalyst is lowered and the hydrogenation rate becomes slower, and a large amount of the catalyst is required, which is not economical, and if the temperature exceeds 150 ° C, side reactions, decomposition and gelation are likely to occur simultaneously, and Hydrogenation of the aromatic portion is also likely to occur and the hydrogenation activity is reduced, which is not preferable. More preferably, it is in the range of 20 to 120 ° C.

The pressure of hydrogen used in the hydrogenation reaction is 1 to 1
00 kg / cm ² is suitable. Since a substantially plateau becomes slower water添速degree is less than 1 kg / cm ² can become difficult to raise the degree of hydrogenation, the pressure exceeding 100 kg / cm ² hydrogenation reaction is substantially complete at the same time as the step-up, substantially It is meaningless and causes unwanted side reactions and gelation, which is not preferable. More preferable hydrogenated hydrogen pressure is 2 to 30 kg /
Although it is cm ² , the optimum hydrogen pressure is selected in consideration of the amount of catalyst added and the like, and it is preferable that the hydrogen pressure is selected on the high pressure side in practice as the amount of the suitable catalyst decreases.

The hydrogenation reaction time of the present invention is usually several seconds to 50 hours. The hydrogenation reaction time is appropriately selected within the above range by other hydrogenation reaction time. By the method of the present invention, the hydrogenation rate of the olefinic unsaturated double bond in the conjugated diene-based copolymer and the copolymer of the conjugated diene and the vinyl aromatic hydrocarbon can be arbitrarily adjusted according to the purpose. A hydrogenation rate of 95% or more is sufficiently possible.

From the solution subjected to the hydrogenation reaction using the catalyst of the present invention, the hydrogenated target substance can be easily separated by chemical or physical means such as distillation or precipitation. In particular,
From the polymer solution which has been subjected to the hydrogenation reaction by the method of the present invention, the catalyst residue can be removed if necessary, and the hydrogenated polymer can be easily isolated from the solution. For example, a method of adding a polar solvent which is a poor solvent for the hydrogenated polymer such as acetone or alcohol to the reaction solution after hydrogenation to precipitate and recover the polymer, and after adding the reaction solution to hot water with stirring, the solvent is added. It can be carried out by a method of distilling and recovering together with it, or a method of directly heating the reaction solution to distill off the solvent.

The hydrogenation method of the present invention is characterized in that the amount of the hydrogenation catalyst used is smaller. Therefore, even if the hydrogenated catalyst remains in the polymer as it is, it does not significantly affect the physical properties of the obtained hydrogenated polymer, and most of the catalyst is decomposed and removed during the isolation process of the hydrogenated polymer. Since it is removed, no special operation for deashing or removing the catalyst is required and it can be carried out by a very simple process. Secondly, the storage stability is extremely excellent. Therefore, the activity of the catalyst can be maintained almost as it was even after several months.

[0081]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto. The production examples of the hydrogenation catalyst and the conjugated diene polymer used for carrying out the examples are shown below. [Example of Hydrogenation Catalyst Synthesis] <Production Example 1> Bis (η ⁵ -cyclopentadienyl) titanium di (p
Tolyl) (catalyst A) synthesis 200 ml of anhydrous ether were added to a 1 liter three-necked flask equipped with a stirrer, a dropping funnel and a reflux condenser. Dry the device with dry helium, lithium wire-piece 1
7.4 g (2.5 mol) was cut into a flask, a small amount of a solution of 300 ml of ether and 171 g (1 mol) of p-bromotoluene was added dropwise at room temperature, and then gradually p was added under reflux.
-The entire ether solution of bromotoluene was added. After completion of the reaction, the reaction solution was filtered under a helium atmosphere to obtain a colorless and transparent p-tolyllithium solution.

A 2-liter three-necked flask equipped with a stirrer replaced with dry helium, a dropping funnel, and bis (η ⁵ -cyclopentadienyl) titanium dichloride 99.6 g (0.4
Mol) and 500 ml of anhydrous ether were added. The ether solution of p-tolyllithium synthesized above was added dropwise under stirring at room temperature for about 2 hours. The reaction mixture was filtered in air, the insoluble portion was washed with dichloromethane, the filtrate and the washing liquid were combined, and the solvent was removed under reduced pressure. After the residue was dissolved in a small amount of dichloromethane, petroleum ether was added for recrystallization. The obtained crystals were separated by filtration, the filtrate was concentrated again, and the above operation was repeated to obtain bis (η ⁵ -cyclopentadienyl) titanium di (p-tolyl). Yield 87%
Met. The obtained crystals are orange-yellow needles, have good solubility in toluene and cyclohexane, and have a melting point of 145 ° C. and elemental analysis values: C, 80.0, H, 6.7, T.
i, 13.3.

<Production Example 2> Bis (η ⁵ -cyclopentadienyl) titanium di ( phenyl )
Synthesis of (phenyl) (catalyst B) Synthesis was conducted in the same manner as in Production Example 1, except that 157 g (1 mol) of bromobenzene was used instead of p-bromotoluene.
Obtained phenyllithium. The following synthesis is performed in exactly the same way,
Bis (η ⁵ -cyclopentadienyl) titanium diphenyl was obtained. The yield was 120 g (yield 90%).
The crystals obtained were in the form of needles of orange yellow color, had a slightly good solubility in toluene and cyclohexane, and had a melting point of 147.
℃, elemental analysis value: C, 79.5, H, 6.1, Ti, 1
It was 4.4.

<Production Example 3> Bis (η ⁵ -cyclopentadienyl) titanium di
Synthesis of (3,4-xylyl) (catalyst C) In Production Example 1, p-bromotoluene was replaced with 4-bromo-
Synthesis was performed in the same manner except that o-xylene (1 mol) was used to obtain bis (η ⁵ -cyclopentadienyl) titanium di (3,4-xylyl). The yield was 83%.
The obtained crystals are yellow needle crystals, have good solubility in toluene and cyclohexane, and have a melting point of 155 ° C.
Elemental analysis values: C, 80.6, H, 7.2, Ti, 12.
It was 2.

[Example of Polymerization of Conjugated Diene Polymer] <Production Example 4> Polymerization of butadiene homopolymer (Polymer-A) 500 g of cyclohexane in 2 l of autoclave,
1,3-Butadiene monomer-100 g, n-butyllithium 0.05 g and tetrahydrofuran 0.6 g were added and polymerized under stirring at 60 ° C. for 3 hours to obtain a butadiene homopolymer. Inactivate the active end with t-butanol,
Vacuum drying was performed at 0 ° C. for 12 hours. The obtained butadiene polymer contained 38% of 1,2-vinyl bonds and had a weight average molecular weight of about 150,000 as measured by GPC. When the active end is deactivated with t-butanol, t-butoxylithium is liberated and the compound functions as the component (E).

<Production Example 5> Polymerization of butadiene / styrene random copolymer (polymer
-B) 400 g of cyclohexane in 2 l of autoclave,
70 g of 1,3-butadiene monomer, styrene monomer
30 g, n-butyllithium 0.03 g and tetrahydrofuran 0.9 g were added, and the mixture was polymerized at 40 ° C. for 2 hours with stirring to obtain a butadiene / styrene copolymer. The active end was inactivated with methanol, and vacuum drying was performed at 60 ° C. for 12 hours. The obtained copolymer was a completely random copolymer of butadiene / styrene, and the content of 1,2-vinyl bonds in the butadiene unit was 53%, and the weight average molecular weight measured by GPC was about 190,000. When the active end is deactivated with methanol, methoxylithium is liberated, and the compound is (E)
Functions as an ingredient.

<Production Example 6> Weight of styrene-butadiene-styrene block copolymer
Compound (Polymer-C) 4000 g of cyclohexane in 7 l of autoclave,
Styrene monomer-150 g and n-butyl lithium 1.1
0 g and 25 g of tetrahydrofuran were added, and the mixture was stirred with stirring at 60
Polymerization was carried out at 0 ° C for 3 hours, then 700 g of 1,3-butadiene monomer was added and polymerization was carried out at 60 ° C for 3 hours. Finally, 150 g of styrene monomer was added and polymerization was carried out at 60 ° C. for 3 hours. The active end was inactivated with water, and vacuum drying was performed at 60 ° C. for 12 hours. The obtained styrene-butadiene-styrene copolymer was a complete block copolymer having a bound styrene content of 30%, a 1,2-vinyl bond content of butadiene units of 45%, and a weight average molecular weight measured by GPC of about 6%. It was good.

(Examples 1 to 3) Polymer-C polymerized in Production Example 6 as a conjugated diene-based polymer was purified and dried to a pressure-resistant autoclave of 250 ml in which a plurality of hydrogen atoms had been substituted with hydrogen to obtain 5.0 g each. It was added as a cyclohexane solution (solution concentration 5 wt%). As catalyst component (A), 0.0125 mmol of each of catalyst A, catalyst B and catalyst C synthesized in Production Examples 1 to 3 was dissolved in 50 ml of cyclohexane, and 0.1 mmol of sec-butyllithium was contained as catalyst component (B). In the presence of 1.8 g of liquid 1,2-polybutadiene (Nisso B-1000: 1,2-vinyl bond amount 85%) manufactured by Nippon Soda Co., Ltd. as a catalyst component (C) with a cyclohexane solution at 25 ° C. and hydrogen pressure. 2.0k
A catalyst solution (n-) mixed for about 30 minutes under an atmosphere of g / m ^2.
BuLi / Ti molar ratio = 8.0) and n-butanol, tetramethylene ethylenediamine as a catalyst component (D),
A cyclohexane solution containing 0.15 mmol each of glycidyl methacrylate was added.

Immediately, 1/3 volume of each catalyst mixed solution was poured into a pressure resistant autoclave containing a polymer solution,
It was pressurized at a hydrogen pressure of 7.0 kg / m ² . The hydrogenation reaction was carried out at 60 ° C. for 1 hour with stirring. After completion of the reaction, the temperature was returned to room temperature and atmospheric pressure, the polymer solution was precipitated in a large amount of methanol, filtered, dried and recovered. Hydrogenation rate is ¹ H-NMR before and after hydrogenation
It was determined by comparing the spectra. The results are shown in Table 1 and Table 2, respectively.

(Examples 4 to 6) The remaining 2/3 volume of the catalyst mixed solution used in Examples 1 to 3 was stored in a hydrogen atmosphere at room temperature for 2 months. 1 of this stored catalyst solution
The hydrogenation reaction was carried out under the same polymer conditions as those of Examples 1 to 3 with a volume of / 2. The results are shown in Table 1 and Table 2, respectively.

(Examples 7 to 9) The rest of the catalyst mixed solution used in Examples 4 to 6 was stored as it was in a hydrogen atmosphere at room temperature for 2 months (4 months from the time of catalyst preparation). The entire amount of this stored catalyst solution was subjected to hydrogenation reaction under the same polymer conditions as in Examples 1 to 6. The results are shown in Table 1 and Table 2, respectively.

Comparative Examples 1-2 As catalyst component (A), 0.0125 mmol of catalyst B synthesized in Preparation Example 2 was dissolved in 50 ml of cyclohexane to prepare n as catalyst component (B).
-Cyclohexane solution containing 0.1 mmol of butyllithium as a catalyst component (C), 1.8 g of liquid 1,2-polybutadiene (B-700: 1,2-vinyl bond amount 57%) manufactured by Nippon Petrochemical Co., Ltd. In the presence of 25 ° C., hydrogen pressure 2.
The catalyst solution (n-BuLi / Ti molar ratio = 8.0) was prepared by mixing in an atmosphere of 0 kg / m ² for about 30 minutes. This catalyst mixed solution was stored for 2 months, and 1/3 volume was poured into a pressure resistant autoclave containing a polymer solution as in Example 7, and the same polymer as in other Examples and Comparative Examples, The hydrogenation reaction was carried out under the conditions. Further, the remaining 1/2 volume of the catalyst mixed solution stored at room temperature for 2 months (4 months from the time of catalyst preparation) was subjected to hydrogenation reaction under exactly the same polymer conditions. The results are shown in Table 1 and Table 2, respectively.

Comparative Examples 3 to 4 0.0125 mmol of the catalyst A synthesized in Preparation Example 1 as a catalyst component (A) was dissolved in 50 ml of cyclohexane, and a cyclohexane solution containing 0.1 mmol of tolyllithium as a catalyst component (B) was prepared. In addition, a cyclohexane solution containing 0.15 mmol of n-heptanol was added to this catalyst solution (tolyllithium / Ti molar ratio = 8.0) as a catalyst component (D) with stirring, and the hydrogen pressure was 25 ° C. The catalyst mixed solution was prepared by mixing in an atmosphere of 2.0 kg / m ² for about 30 minutes. This catalyst mixed solution was stored for 2 months, and 1/3 of the volume was held in a pressure resistant autoclave containing a polymer solution as in the other examples and comparative examples.
The mixture was then put into a bath and hydrogenated. Further, the remaining 1/2 volume of the catalyst mixed solution stored at room temperature for 2 months (4 months from the time of catalyst preparation) was subjected to hydrogenation reaction under exactly the same polymer conditions. The results are shown in Table 1 and Table 2, respectively.

(Comparative Example 5) The procedure of Example 4 was repeated except that the catalyst component (B) was added last. The results are shown in Table 1 and Table 2, respectively.

[0095]

[Table 1]

[0096]

[Table 2]

(Examples 10 to 11) As a catalyst component (A), 0.0125 mmol of the catalyst A synthesized in Preparation Example 1 was dissolved in 50 ml of cyclohexane, and cyclohexane containing 0.1 mmol of sec-butyllithium as a catalyst component (B). Using the solution as the catalyst component (C), liquid 1,2-polybutadiene (Nisso B-100, manufactured by Nippon Soda Co., Ltd.)
0: 1,2-vinyl bond amount 85%) in the presence of 1.8 g,
In addition, the mixture was stirred and mixed under an atmosphere of 25 ° C. and hydrogen pressure of 2.0 kg / m ² for about 30 minutes. Furthermore, this catalyst solution (sec-B
A cyclohexane solution containing 0.15 mmol of t-butanol as a catalyst component (D) was added to uLi / Ti molar ratio = 8.0) with stirring to prepare a catalyst mixed solution. This catalyst mixed solution was stored for 4 months, and 250 ml pressure-resistant autoclave containing 5.0 g of each A polymer and B polymer solution (5 wt% cyclohexane solution) was stored in 1/3 volume.
Then, the reaction was carried out in exactly the same manner as in the other examples and comparative examples. The results are shown in Tables 3 and 4 together with Example 7.
Shown in

(Example 12) The same procedure as in Example 10 was carried out except that 0.05 mmol of ethylbutyl magnesium (EBM) was used as the catalyst component (B). The results are shown in Tables 3 and 4.
Shown in (Example 13) The same procedure as in Example 12 was repeated except that 0.04 mmol of ethylbutyl magnesium (EBM) and 0.01 mmol of triethylaluminum were used as the catalyst component (B). The results are shown in Tables 3 and 4. Comparative Example 6 Liquid polybutadiene (R-45H: 1, manufactured by Idemitsu Petrochemical Co., Ltd.) was used as the catalyst component (C) in Example 10.
The same procedure was performed except that 2-vinyl bond amount 23%) was used. The results are shown in Tables 3 and 4.

[0099]

[Table 3]

[0100]

[Table 4]

[0101]

As described above, by employing the catalyst and method of the present invention, the olefinicity of the conjugated diene moiety of the olefin compound / conjugated diene polymer or the polymer of the conjugated diene and the vinyl aromatic hydrocarbon is improved. It has become possible to highly selectively hydrogenate unsaturated double bonds to a high position. In addition, the storage stability of the catalyst is dramatically improved, and it can be handled stably without being easily affected by the catalyst preparation state and impurities in the system, and the trouble of preparing the catalyst immediately before hydrogenation can be avoided.
It also streamlines the process. Further, the method of the present invention can be applied to continuous hydrogenation. The hydrogenated polymer obtained by the method of the present invention is used as an elastic body excellent in weather resistance and oxidation resistance, a thermoplastic elastic body or a thermoplastic resin, and further contains an ultraviolet absorber, an oil, a filler and the like. Used by adding agents or blending with other elastic bodies and resins,
It is extremely useful industrially.

Claims (6)

[Claims] 1. A method comprising the following components (A) to (D), which is prepared by reducing (A) with (B) in the presence of (C) and then adding (D). A composite catalyst for hydrogenating an olefin compound. (A) At least one of the titanocene compounds represented by the following general formula (1). Embedded image (However, R ¹ and R ² represent a group selected from a C _{1 to} C ₁₂ hydrocarbon group, an aryloxy group, an alkoxyl group, a halogen group, and a carbonyl group, and R ¹ and R ² are the same. Cp represents a cyclopentadienyl group.) (B) Li-containing, Na, K, Mg, B having reducing ability
At least one reducing agent selected from a, Zn, Al and Ca compounds. (C) An olefinic unsaturated double bond-containing polymer in which the ratio of the amount of side chain olefinic unsaturated double bonds to the total amount of olefinic unsaturated double bonds is 0.3 to 1. (D) Alcohol compound, ether compound, thioether compound, ketone compound, sulfoxide compound, carboxylic acid compound, carboxylic acid ester compound, aldehyde compound, lactone compound, amine compound, amide compound,
At least one polar compound selected from the group of nitrile compounds, epoxy compounds and oxime compounds. 2. A method comprising the following components (A) to (E), wherein (A) is reduced with (B) in the presence of (C) and (E), and then (D) is added to prepare the mixture. A composite catalyst for hydrogenating an olefin compound, characterized by: (A) At least one of the titanocene compounds represented by the following general formula (1). Embedded image (However, R ¹ and R ² represent a group selected from a C _{1 to} C ₁₂ hydrocarbon group, an aryloxy group, an alkoxyl group, a halogen group, and a carbonyl group, and R ¹ and R ² are the same. Cp represents a cyclopentadienyl group.) (B) Li-containing, Na, K, Mg, B having reducing ability
At least one reducing agent selected from a, Zn, Al and Ca compounds. (C) An olefinic unsaturated double bond-containing polymer in which the ratio of the amount of side chain olefinic unsaturated double bonds to the total amount of olefinic unsaturated double bonds is 0.3 to 1. (D) Alcohol compound, ether compound, thioether compound, ketone compound, sulfoxide compound, carboxylic acid compound, carboxylic acid ester compound, aldehyde compound, lactone compound, amine compound, amide compound,
At least one polar compound selected from the group of nitrile compounds, epoxy compounds and oxime compounds. (E) An alkaline compound represented by the following general formula (2). R ³ OM (2) (where M is at least one alkali metal atom selected from lithium, sodium and potassium. R ³ is C ₁
To C ₁₂ alkyl group, aryl group, aralkyl group or hydrocarbon group having oxygen atom and / or nitrogen atom. ) 3. A method comprising the following components (A) to (E), wherein (A) is reduced with (B) in the presence of (C), and then (D) and (E) are added to prepare the mixture. A composite catalyst for hydrogenating an olefin compound, which comprises: (A) At least one of the titanocene compounds represented by the following general formula (1). Embedded image (However, R ¹ and R ² represent a group selected from a C _{1 to} C ₁₂ hydrocarbon group, an aryloxy group, an alkoxyl group, a halogen group, and a carbonyl group, and R ¹ and R ² are the same. Cp represents a cyclopentadienyl group.) (B) Li-containing, Na, K, Mg, B having reducing ability
At least one reducing agent selected from a, Zn, Al and Ca compounds. (C) An olefinic unsaturated double bond-containing polymer in which the ratio of the amount of side chain olefinic unsaturated double bonds to the total amount of olefinic unsaturated double bonds is 0.3 to 1. (D) Alcohol compound, ether compound, thioether compound, ketone compound, sulfoxide compound, carboxylic acid compound, carboxylic acid ester compound, aldehyde compound, lactone compound, amine compound, amide compound,
At least one polar compound selected from the group of nitrile compounds, epoxy compounds and oxime compounds. (E) An alkaline compound represented by the following general formula (2). R ³ OM (2) (where M is at least one alkali metal atom selected from lithium, sodium and potassium. R ³ is C ₁
To C ₁₂ alkyl group, aryl group, aralkyl group or hydrocarbon group having oxygen atom and / or nitrogen atom. ) 4. A conjugated diene-based polymer or a copolymer of a conjugated diene and a vinyl aromatic hydrocarbon is brought into contact with hydrogen in an inert organic solvent to obtain an olefinically unsaturated double bond of the polymer. When hydrogenating, the compound catalyst according to any one of claims 1 to 3 is prepared in advance in a catalyst tank and transferred to the hydrogenation tank to be used as the catalyst for hydrogenation. A method for producing a conjugated diene polymer. 5. A conjugated diene-based polymer or a copolymer of a conjugated diene and a vinyl aromatic hydrocarbon is brought into contact with hydrogen in an inert organic solvent to obtain an olefinically unsaturated double bond of the polymer. A method for producing a hydrogenated conjugated diene polymer, which comprises using the composite catalyst according to claim 2 or 3 as a catalyst for the hydrogenation when hydrogenating. 6. A conjugated diene polymer or a polymer of a conjugated diene and a vinyl aromatic hydrocarbon has a conjugated diene moiety of 1,3-butadiene and / or isoprene and a vinyl aromatic hydrocarbon of styrene and / or Alternatively, it is α-methylstyrene, and the method for producing a hydrogenated conjugated diene polymer according to claim 4 or 5.