JPH0827216A - Hydrogenation of alkyl group-substituted conjugated diene-based polymer - Google Patents

Abstract

PURPOSE:To obtain a hydrogenated conjugated diene-based polymer excellent in weather and oxidation resistances by using a specific stable and readily handleable titanocene-based highly active hydrogenation catalyst capable of withstanding the storage for a long period and manifesting activities with good reproducibility in hydrogenation with a trace amount thereof. CONSTITUTION:This method for hydrogenating an alkyl group-substituted conjugated diene-based polymer is to use a catalyst comprising (A) a titanocene compound of the formula (R<1> and R<2> are each a 1-12C hydrocarbon, etc.; Cp is cyclopentadienyl ring), (B) a reducing agent, having reducing power and selected from an organomagnesium, an organozinc and an organoaluminum compounds, (C) a polymer having 0.3-1 fraction of olefinic unsaturated bonds in the side chain to the whole and 500-10000 number-average molecular weight and (D) an alcohol of the formula ROH (R is a 1-20C hydrocarbon) at 0.05-5 ratio of the components (A)/(B) and 0.05-10 ratio of the components (D)/(B), in bringing a conjugated diene-based polymer which is a monomer unit constituting a polymer chain in which 1-2 of two carbon atoms having an olefinic unsaturated bond are substituted with a 1-18C alkyl or a copolymer of the conjugated diene and a vinyl aromatic hydrocarbon into contact with hydrogen in an inert organic solvent and hydrogenating the olefinic unsaturated double bonds.

Description

Detailed Description of the Invention

[0001]

The present invention relates to a monomer unit constituting a polymer chain, wherein one or two of the two carbons having an olefinically unsaturated double bond are C _{1 to} C ₈ An olefinically unsaturated diene polymer in a conjugated diene polymer substituted with an alkyl group or a copolymer of a conjugated diene having an alkyl substituent other than the main chain in an olefinically unsaturated double bond and a vinyl aromatic hydrocarbon The present invention relates to a hydrogenation method capable of selectively hydrogenating a heavy bond.

[0002]

2. Description of the Related Art 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 a large amount of catalyst is required to carry out the desired hydrogenation reaction. It will be uneconomical because it is exposed On the other hand, the latter homogeneous catalyst has a characteristic that it can be hydrogenated at a lower temperature and a lower pressure, since the hydrogenation reaction usually proceeds in a homogeneous system, so the activity is high and the amount of the catalyst used is small compared to the heterogeneous system. In the case of hydrogenating an olefinically unsaturated double bond substituted with an alkyl group having steric hindrance, sufficient hydrogenation activity has not been obtained. Therefore, under these circumstances, there is a strong demand for the development of hydrogenation catalysts which are highly active and easy to handle.

In the polymer containing an olefinically unsaturated double bond, the unsaturated double bond is advantageously used for vulcanization and the like, while such a double bond is stable in heat resistance and oxidation resistance. It has inferior drawbacks. 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 the polymer, compared with the case of hydrogenating the low molecular weight compound, it becomes difficult to hydrogenate due to the influence of the viscosity of the reaction system and the steric hindrance of the polymer chain. Further, there is a drawback in that it is extremely difficult to physically remove the catalyst after hydrogenation is completed, and the catalyst cannot be practically completely separated. Therefore, in order to hydrogenate the polymer in an economically advantageous manner, 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 in combination with an aluminum, organozinc, or organomagnesium compound (JP-A 61-28507, 62-20910).
No. 3), a method of hydrogenating a living polymer containing an olefinically unsaturated double bond with a combination of a specific titanocene compound and an alkyllithium (JP-A-61-47706).
Japanese Patent Laid-Open No. 63-5402) and the like have already been invented.

Although these methods allow hydrogenation to a high level, it is difficult to handle the hydrogenation catalyst and the long-term storage stability is also difficult. Therefore, in order to solve this, a method of hydrogenating an olefin compound with a combination of a specific titanocene and a reducing agent in the presence of a liquid rubber having a specific microstructure was invented (JP-A-4-96905). In addition, a catalyst composition was filed in which the storage stability of the catalyst was dramatically improved by further adding alcohol to the catalyst composition (Japanese Patent Application No. 6-103970). However, in this method, the activity is not sufficient for hydrogenating an alkyl-substituted olefinically unsaturated double bond having steric hindrance, and since a large amount of catalyst is required, a method for reducing the amount of the catalyst is desired. Was there.

US Pat. No. 5,243,986 discloses a styrene-butadiene-isoprene or butadiene-isoprene copolymer which is an olefinically unsaturated double bond in the polybutadiene moiety in the presence of a specific titanocene compound and a reducing agent. It is disclosed that only 1,2 or 3,4 bond of the side chain of the polyisoprene moiety is selectively hydrogenated, and in the titanocene compound, 1,4 or 1,4 of the polyisoprene moiety is selectively hydrogenated.
It is disclosed that the bond is difficult to hydrogenate.

[0007]

The present invention is stable and easy to handle, can withstand long-term storage, exhibits reproducible activity with a very small amount used during hydrogenation reaction, and has sterically hindered alkyl-substituted unsaturated double bonds. By using a titanocene-based highly active hydrogenation catalyst that can hydrogenate the bonds even in an amount that does not require deashing, a polymer hydrogenated product with excellent weather resistance, oxidation resistance, and ozone resistance can be obtained. The challenge is to find a way.

As a result of diligent studies on the above problems, the inventors of the present invention reduced at least one titanocene compound (A) having a specific structure selected from an organomagnesium compound, an organozinc compound and an organoaluminum compound having a reducing ability. Upon reduction with the agent (B), a polymer (C) having an olefinic unsaturated double bond in a side chain at a specific ratio or more is made to coexist, and finally R ³ OH (where R ³ is C ₁ to
(Representing a C ₂₀ hydrocarbon group) represented by (D)
(B) of the catalyst compositions obtained by adding
The specific composition of component / (A) component (molar ratio) = 0.05 to 5 and (D) component / (B) component (molar ratio) = 0.05 to 10 is difficult with a conventional titanocene-based catalyst. Was a sterically hindered alkyl-substituted unsaturated double bond,
For example, the unsaturated double bond of 1,4 bond of the polyisoprene unit can be hydrogenated to a high position with a low catalyst amount which does not require deashing
The present invention was made by finding that a hydrogenated product of the polymer having excellent weather resistance and oxidation resistance can be obtained.

[0009]

That is, the present invention is a monomer unit constituting a polymer chain, wherein one or two carbon atoms having two olefinically unsaturated double bonds are C ₁ To a conjugated diene polymer substituted with an alkyl group of C ₈ or a monomer unit constituting a polymer chain, wherein one or two of the two carbons having an olefinically unsaturated double bond are A copolymer of a conjugated diene substituted with a C ₁ -C ₈ alkyl group and a vinyl aromatic hydrocarbon is brought into contact with hydrogen in an inert organic solvent to give an olefinically unsaturated double bond of the polymer. In the presence of (C), which comprises the following components (A) to (D):
A catalyst composition prepared by reducing (A) with (B) and then adding (D) (however, (B) component / (A) component (molar ratio) = 0.05 to 5, and (D)). Component / (B) component (molar ratio) = 0.05 to 10), which is a method for hydrogenating an alkyl group-substituted conjugated diene polymer, wherein (A) is represented by the following formula (1): At least one titanocene compound

[0010]

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(Wherein R ¹ and R ² represent a group selected from a C _{1 to} C ₁₂ hydrocarbon group, an aryloxy group, an alkoxy group, a halogen group and a carbonyl group, and R ¹ and R ²
May be the same or different. Cp represents a cyclopentadienyl ring. ) (B) At least one reducing agent selected from organic Mg compounds, organic Zn compounds, and organic Al compounds having reducing ability (C) All olefinically unsaturated double bonds of side chain olefinically unsaturated double bonds Olefinic unsaturated double bond-containing polymer having a number average molecular weight of 500 or more and 10000 or less and a fraction of 0.3 to 1 (D) An alcohol represented by the following formula (2) (provided that R ³
Represents a C _{1 to} C ₂₀ hydrocarbon group)

[0012]

[Chemical 4]

A method for hydrogenating an alkyl group-substituted conjugated diene polymer is characterized in that the above-mentioned catalyst composition is prepared in advance in a catalyst tank and is transferred to a hydrogenation tank for hydrogenation reaction. . Hereinafter, the present invention will be described in detail. In the present invention, it is a monomer unit constituting a polymer chain to be hydrogenated, and one or two of two carbons having an olefinically unsaturated double bond is a C _{1 to} C ₈ alkyl group. Substituted conjugated diene-based polymer, or a monomer unit constituting a polymer chain, wherein one or two of two carbons having an olefinically unsaturated double bond are C ₁ -C ₈ alkyl. Copolymers of group-substituted conjugated dienes and vinyl aromatic hydrocarbons are particularly useful when the conjugated diene moiety is isoprene.

A compound having at least one of the above formula (1) and a reducing power according to the present invention, and an olefinically unsaturated double bond-containing polymer having a olefinically unsaturated double bond in a side chain at a specific ratio or more. A method of hydrogenating an olefin compound using (C) as a catalyst has already been disclosed in JP-A-4-96905. The inventors of the present invention further improved the activity of the olefin hydrogenation catalyst of the earlier application, and conducted further studies to develop a catalyst composition having excellent storage stability. As a result, the catalyst composition of the invention finally had a specific ratio. An application has already been filed for a hydrogenated catalyst composition in which the storage stability of the catalyst is dramatically improved by the addition of the alcohol compound (D) (Japanese Patent Application No. 6-103970). Then, as described above, a specific reducing agent (B) is selected from the hydrogenated catalyst composition, and the main catalyst, the titanocene compound (A), the reducing agent (B) and the alcohol (D). Only the catalyst composition having the specific composition ((B) component / (A) component (molar ratio) = 0.05 to 5 and (D) component / (B) component = 0.05 to 10) Efficiently and economically also the unsaturated double bond having an alkyl substitution in the main chain, which is difficult to achieve with a titanocene catalyst, has an alkyl substitution in the main chain, for example, the unsaturated double bond of the 1,4 bond part of the polyisoprene part. The inventors have invented a catalyst composition for hydrogenation and completed the present invention.

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

[0016]

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(Wherein R ¹ and R ² represent a group selected from a C _{1 to} C ₁₂ hydrocarbon group, an aryloxy group, an alkoxy group, a halogen group and a carbonyl group, and R ¹ and R ²
May be the same or different. Cp represents a cyclopentadienyl ring. ) In the formula (1), R ¹ and R ² are C ₁ to C ₁₂ hydrocarbon groups, and examples thereof include a substituent represented by the following formula (3).

[0018]

[Chemical 6]

(However, R ^{4 to} R ⁶ are hydrogen or C ₁
To C ₄ alkyl hydrocarbon groups, one of R ^{4 to} R ⁶ is hydrogen, and n = 0 or 1. ) In the formula (3), when R ⁴ to R ⁶ are all alkyl groups, hydrogenation activity is slightly inferior, probably because of steric hindrance, which is not preferable. Further, a compound in which the alkyl hydrocarbon group is in the ortho position with respect to the central metal is not preferable because it is difficult to synthesize although the activity is recognized.

Specific examples of the catalyst (A) include bis (η ⁵ cyclopentadienyl) titanium dimethyl, bis (η ⁵ cyclopentadienyl) titanium diethyl,
Bis (η ⁵ cyclopentadienyl) titanium di-n-butyl, bis (η ⁵ cyclopentadienyl) titanium di-sec-butyl, bis (η ⁵ cyclopentadienyl) titanium dihexyl, bis (η ⁵ cyclopentadienyl) Titanium dioctyl, bis (η ⁵ cyclopentadienyl) titanium dimethoxide, bis (η ⁵ cyclopentadienyl) titanium diethoxide, bis (η
⁵ cyclopentadienyl) titanium diphenyl, bis (η ⁵ cyclopentadienyl) titanium di-m-tolyl, bis (η ⁵ cyclopentadienyl) titanium di (p-tolyl), bis (η ⁵ cyclopentadienyl) titanium Gee m, p Kishiriru, bis (eta ⁵ cyclopentadienyl) titanium di-4-ethylphenyl, bis (eta ⁵ cyclopentadienyl) titanium di-4-hexylphenyl, bis (eta ⁵ cyclopentadienyl) titanium diphenoxide, Bis (η ⁵ cyclopentadienyl) titanium difluoride, bis (η ⁵ cyclopentadienyl) titanium dibromide, bis (η ⁵ cyclopentadienyl) titanium diiodide, bis (η
⁵ cyclopentadienyl) titanium chloride methyl, bis (η ⁵ cyclopentadienyl) titanium chloride ethoxide, bis (η ⁵ cyclopentadienyl) titanium chloride phenoxide, bis (η ⁵ cyclopentadienyl) titanium dibenzyl, etc. Is mentioned. These can be used alone or in combination with each other.

Of these titanocene compounds, preferred are those which have a high hydrogenation activity for the olefinic unsaturated double bond in the olefin compound and which can selectively hydrogenate the unsaturated double bond satisfactorily under mild conditions. , Bis (η ⁵ cyclopentadienyl) titanium dimethyl, bis (η ⁵
Cyclopentadienyl) titanium di-n-butyl, bis (η ⁵ cyclopentadienyl) titanium di (p-
And tris), bis (η ⁵ cyclopentadienyl) titanium dichloride, bis (η ⁵ cyclopentadienyl) titanium dicarbonyl, and bis (η ⁵ cyclopentadienyl) titanium diphenyl.

More preferable ones, which can be handled more stably and are most likely to exhibit the activity when combined with the reducing metal compound (B), are bis (η ⁵ cyclopentadienyl) titanium dichloride and bis (η). ⁵ cyclopentadienyl) titanium diphenyl and bis (η ⁵ cyclocyclocyclopentadienyl) titanium di-p-tolyl, the latter being the most preferable because they have excellent solubility in a solvent.

On the other hand, as the catalyst component (B), among the organometallic compounds and metal-containing compounds capable of reducing the titanocene compound of the catalyst component (A), organozinc compounds, organomagnesium compounds, organoaluminum compounds, etc. The polymers can be hydrogenated by using them alone or in combination with two or more kinds (A).

Examples of organic zinc compounds include diethyl zinc, bis (η ⁵ cyclopentadienyl) zinc, diphenyl zinc and the like. Further, as an organomagnesium compound, dimethylmagnesium, diethylmagnesium, dibutylmagnesium, dialkylmagnesium compounds such as ethylbutylmagnesium, methylmagnesium bromide, ethylmagnesium chloride, ethylmagnesium bromide, butylmagnesium chloride,
Phenylmagnesium bromide, phenylmagnesium chloride, s-butylmagnesium chloride, t
-A Grignard reagent such as butyl magnesium chloride.

Further, as the organic aluminum compound,
Trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, triphenyl aluminum, dimethyl aluminum chloride, diethyl aluminum chloride, ethyl aluminum dichloride, methyl aluminum sesquichloride, ethyl aluminum sesquicloloid, diethyl aluminum hydride, diisobutyl aluminum hydride, triphenyl aluminum, tri ( 2-ethylhexyl) aluminum, (2-
Ethylhexyl) aluminum dichloride, methylaluminoxane, ethylaluminoxane and the like.

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. In order to selectively hydrogenate an alkyl-substituted olefinically unsaturated double bond having the highest hydrogenation activity and having steric hindrance,
Most preferred are organomagnesium compounds such as ethylbutyl magnesium, dibutyl magnesium, phenyl magnesium chloride and phenyl magnesium bromide.

The catalyst component (C) has a number average molecular weight of not less than 500 and a fraction of 0.3 to 1 with respect to the total amount of olefinically unsaturated double bonds in the side chain olefinically unsaturated double bonds.
Examples of monomers used to make polymers containing 0000 or less olefinically unsaturated double bonds include conjugated dienes, typically conjugated dienes having from 4 to about 12 hydrocarbons. As a specific example, 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 and the like can be 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 copolymers are preferred. Further, norbornadiene, pentadiene, 2,3-dihydrodipentadiene and alkyl-substituted products thereof may be used alone or as a copolymer.

The number average molecular weight of the polymer of the catalyst component (C) is 500 or more and 10,000 or less. Number average molecular weight is 50
If it is less than 0, the stabilizing effect of the reduced catalyst is small, so a liquid rubber having a number average molecular weight of 500 or more, which is liquid at room temperature, is desirable because it is easy to handle. Number average molecular weight is 1000
When it is 0 or more, handling as a liquid becomes difficult, and the physical properties of the alkyl group-substituted conjugated diene polymer to be hydrogenated may be adversely affected, which is not preferable. The microstructure of the polymer of the catalyst component (C) is important. That is, “the fraction of side chain olefinically unsaturated double bonds to the total olefinically unsaturated double bonds”
Is defined as follows.

[Number of olefinically unsaturated carbon-carbon double bonds in the side chain of component (C) polymer] / [total number of olefinic unsaturated carbon-carbon double bonds of component (C) polymer] This value Is essential to be 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. As a specific example, when the catalyst component (C) is polybutadiene, all olefinically unsaturated double bonds (cis 1,4 bond, trans 1,
It means that the olefinically unsaturated double bond (1,2 bond) of the side chain is in the range of 0.3 to 1 with respect to 4 bonds, 1,2 bond. If this ratio is less than 0.3, the reduced catalyst becomes unstable and difficult to handle, and storage stability may be poor, which is not preferable.

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, α-
Methylstyrene, p-methylstyrene, divinylbenzene, 1,1-diphenylethylene, N, N-diethyl-
Examples thereof include p-aminoethylstyrene, 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 are random,
It may be a block, a star block, a tapered block, or the like, and is 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. As a result, a relatively large amount of the catalyst component (C) is required, which may change the physical properties of the hydrogenated conjugated diene polymer and the conjugated diene and vinyl aromatic hydrocarbon copolymer, which is not preferable.

Most importantly, the ratio of the olefinically unsaturated double bonds in the side chain of the conjugated diene moiety to the total olefinic double bonds is required to be 0.3 to 1, and the preferable ratio is It 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 anion polymerization, or by coordination anion polymerization with a cobalt-based Ziegler type catalyst, or ethylene and dicyclopentadiene compounds. Can be obtained by copolymerization.

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. Further, as an organolithium compound-based catalyst, methyllithium, ethyllithium, n-propyllithium, isopropyllithium, n
-Butylium, sec-butyllithium, isobutyllithium, tert-butyllithium, n-pentyllithium, n-hexyllithium, trimethylsilyllithium and the like.

Methyl sodium, ethyl sodium, n-propyl sodium, isopropyl sodium, n-butyl sodium as an organic sodium compound catalyst,
Examples thereof include sec-butyl sodium, isobutyl sodium, phenyl sodium, sodium naphthalene, and cyclopentadienyl sodium. Catalyst component (D)
Is at least one compound selected from alcohols represented by the following formula (2).

[0035]

[Chemical 7]

(Wherein R ³ represents a C _{1 to} C ₂₀ hydrocarbon group) In the formula (2), the hydrocarbon group means a C _{1 to} C ₂₀ alkyl group, a phenyl group, an alkoxy group, an aryl group, An aryloxy group and the like are included. Therefore, any compound containing a hydroxyl group may be a nitrogen-containing, sulfur-containing or phosphorus-containing compound.
Specific examples of the catalyst component (D) include methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, butyl alcohol, isobutyl alcohol, sec-butyl alcohol, tert-butyl alcohol, n-amyl alcohol, isoamyl alcohol, hexyl alcohol, heptyl alcohol, octyl alcohol, capryl alcohol, nonyl alcohol, decyl alcohol, benzyl alcohol, phenol, cresol, 2,6- Di-tert-butyl-p
-Monohydric alcohol such as cresol, ethylene glycol, propylene glycol, butanediol, pentyl glycol, hexyl glycol, heptyl glycol,
Examples thereof include octyl glycol and glycols (dihydric alcohols) which are isomers thereof. Further, it may be a compound containing other functional group such as trihydric alcohol such as glycerin or ethanolamine. Preferred examples of the catalyst component (D) include aliphatic alcohols such as methyl alcohol, ethyl alcohol and butyl alcohol.

The present invention is a monomer unit constituting a polymer chain, wherein one or two of two carbons having an olefinically unsaturated double bond are substituted with a C ₁ -C ₈ alkyl group. Conjugated diene polymer, or a monomer unit constituting a polymer chain, wherein one or two of two carbons having an olefinically unsaturated double bond is a C ₁ -C ₈ alkyl group. It is applied to the selective hydrogenation of olefinically unsaturated double bonds of a copolymer of a conjugated diene substituted with a and a vinyl aromatic hydrocarbon, but, of course, it is applicable to a conventional conjugated diene-based polymer (for example, polybutadiene). Is also applicable. These hydrogenated products are industrially useful as elastic bodies and thermoplastic elastic bodies.

In the conjugated diene polymer of the present invention, one or two of the two carbons having an olefinic unsaturated double bond are C units which are monomer units constituting a polymer chain.
Conjugated diene homopolymer substituted with _{1 to} C ₈ alkyl group, conjugated diene copolymer, copolymer with non-alkyl group substituted conjugated diene (for example, 1,3-butadiene), isoprene-isobutylene copolymer An example is coalescence.

In the monomer unit constituting such a polymer chain, a conjugation in which one or two of two carbons having an olefinically unsaturated double bond are substituted with a C ₁ -C ₈ alkyl group. The alkyl-substituted conjugated diene used in the production of the diene polymer is represented by the following formulas (4) and (5), and R ⁷ , R ⁸ and R ⁹ are C _{1 to} C ₈ hydrocarbon groups, R ⁸ and R
⁹ may be the same or different.

[0040]

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[0041]

[Chemical 9]

Generally mentioned are alkyl-substituted conjugated dienes having from 5 to about 12 carbon atoms, specific examples being isoprene, 2,3-dimethyl-1,3-butadiene, 1-pentadiene. , 2-methyl-1,3-pentadiene, 1,3-hexadiene, 4,5-diethyl-
1,3-octadiene and 3-butyl-1,3-octadiene. Isoprene is preferred from the standpoint of obtaining an elastic body that can be industrially developed and has excellent physical properties.
Of course, 1,3-butadiene may also be copolymerized as the conjugated diene.

Besides, it can be applied to hydrogenation of polymers such as natural rubber and isoprene / isobutylene rubber (IIR).
The microstructure of the polybutadiene portion has 1,2 bonds and 1,4 bonds (cis + trans), and both of the catalysts of the present invention can be quantitatively hydrogenated. Also,
In the polyisoprene 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). Bond), formula (7) (3,4 bond), and formula (8) (1,4 bond).

[0044]

[Chemical 10]

[0045]

[Chemical 11]

[0046]

[Chemical 12]

The structure and hydrogenation rate can be measured by ¹ H-NMR as described later.
Using the method of the present invention, 1,2 bonds of the butadiene moiety,
1,4 bond and 1,2 bond of isoprene moiety: (6)
Formula, 3,4 bond: Not only Formula (7), 1,4 bond:
Formula (8) can also be hydrogenated at a high level. In the usual anionic polymerization with alkyllithium, 1,2 bonds are 0%, 3,4 bonds are 5-10% in a non-polar solvent.
It is known that 1,4 bonds account for 90 to 95%, but in particular, the method of the present invention is an isoprene polymer obtained by living anionic polymerization, and an olefin of a polyisoprene moiety in an isoprene / styrene copolymer. It is effective for selectively hydrogenating the unsaturated unsaturated double bond.

Further, as the olefin monomer copolymerizable with at least one of the alkyl group-substituted conjugated dienes,
Vinyl-substituted aromatic hydrocarbons are particularly desirable because they are industrially useful and can be used for valuable elastic bodies and thermoplastic elastic bodies. Specific examples of such vinyl-substituted aromatic hydrocarbons include styrene, tert-butylstyrene, α-methylstyrene, p-methylstyrene, divinylbenzene,
1,1-diphenylethylene, N, N-dimethyl-p-
Aminoethylstyrene, N, N-diethyl-p-aminostyrene and the like can be mentioned, with styrene and / or styrene being particularly preferred. The most preferable example of the copolymer is a butadiene / isoprene copolymer, an isoprene / styrene copolymer, a butadiene / isoprene / styrene copolymer, and the like because they give a hydrogenated copolymer having a high industrial value. Is. These copolymers may be random, block or tapered block copolymers.

A preferred embodiment of the hydrogenation reaction of the present invention is
It is carried out in 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, n-pentane, n-hexane, n-
These are aliphatic hydrocarbons such as heptane and n-octane, alicyclic hydrocarbons such as cyclohexane, cycloheptane and cycloheptane, and ethers such as diethyl ether and tetrahydrofuran, either alone or in a mixture. Also, aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene can be used only when 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 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. Nitrogen acts as a catalyst poison during the hydrogenation reaction and may reduce the hydrogenation activity, which is not preferable. In particular, it is most preferable that the hydrogenation reactor has an atmosphere of hydrogen gas alone.

On the other hand, the catalyst is prepared by reducing the catalyst component (A) with the catalyst component (B) in the presence of the catalyst component (C) in an inert organic solvent, and finally adding the catalyst component (D). To prepare. In addition to the inert atmosphere, the reducing atmosphere is
Hydrogen may be used. The reduction temperature and the storage temperature are -5.
It is from 0 ° C to 50 ° C, particularly preferably from -20 ° C to 30 ° C. The time required for the reduction varies depending on the reduction temperature, but it is 5 minutes to 60 days at 25 ° C, and 5 minutes to 20 days.
Day is preferred. Within this range, an alkyl-substituted olefinically unsaturated hydrocarbon having particularly high activity and steric hindrance can be highly hydrogenated.

The catalyst component (B) needs to be handled under the above-mentioned inert atmosphere. The catalyst component (A) does not decompose immediately in air, but it is preferably handled in an inert atmosphere. Catalyst components (A), (B), (C),
It is preferable to use (D) as a solution of an inert organic solvent because it is easy to handle. As the inert organic solvent used when used as a solution, the above-mentioned various solvents used as the hydrogenation reaction solvent can be used. It is preferably the same solvent as that used for the hydrogenation reaction.

When the catalyst component is added to the hydrogenation reactor,
Most preferably, it is carried out under a hydrogen atmosphere. The temperature at the time of addition is -30 ° C to 100 ° C, preferably -1.
It is advisable to add it at a temperature of 0 ° 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 referred to as Meta.
The molar ratio of 1 (B) / Metal (A) is in the range of 0.05 to 5. If the molar ratio of Metal (B) / Metal (A) exceeds 5, it is not preferable because the activity which makes the olefinic unsaturated double bond (8) of the main chain substituted with an alkyl group highly hydrogenated cannot be obtained. Also, this ratio is 0.05
When it is smaller, the reduction rate is slow and it takes a long time for the activity to be exhibited, which is not preferable. Only when this ratio is in the range of 0.05 to 5, the olefinically unsaturated double bond of the alkyl-substituted main chain having steric hindrance, which is difficult to achieve with the conventional titanocene-based catalyst, is hydrogenated to a high position.

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 a part or all of this active end is a catalyst component. It can be used as (B). Therefore, the optimal Metal (B) / Me
In order to achieve the tal (A) molar ratio, it is necessary to inactivate some or all of the active terminals with compounds having various active hydrogens or halogens.

As the compound having such active hydrogen,
Water, and methanol, ethanol, n-propanol, n-butanol, sec-butanol, t-butanol, 1-pentanol, 2-pentanol, 3-pentanol, 1-hexanol, 2-hexanol, 3
Alcohols such as hexanol, 1-heptanol, 2-heptanol, 3-heptanol, 4-heptanol, octanol, nonanol, decanol, undecanol, lauryl alcohol, allyl alcohol, cyclohexanol, cyclopentanol, benzyl alcohol, phenol, o -Cresol, m-cresol, p-cresol, p-allylphenol, 2,6-
Phenols such as di-t-butyl-p-cresol, xylenol, dihydroanthraquinone, dihydroxycoumarin, 1-hydroxyanthraquinone, m-hydroxybenzyl alcohol, resorcinol, leucoaurine, acetic acid, propionic acid, butyric acid, isoacetic acid, pentanoic acid Examples thereof include acids such as organic carboxylic acids such as hexanoic acid, heptanoic acid, decalic acid, myristic acid, stearic acid, behenic acid, and benzoic acid.

As the halogen-containing compound, benzyl chloride, trimethylsilyl chloride (bromide), t-butylsilyl chloride (bromide), methyl chloride (bromide), ethyl chloride (bromide), propyl chloride (bromide), n-
Butyl chloride (bromide) and the like can be mentioned. These may be used alone or in combination of two or more.

The addition amount of the catalyst component (C) is the same as that of the catalyst component (A).
A weight ratio of 10 to 500 is preferable with respect to the above catalyst. 1
If it is less than 0, the effect of stabilizing the storage and reducing the amount of the catalyst becomes small. If this ratio exceeds 500, the hydrogenation activity will be good, but it will be difficult to separate the hydrogenated polymer and the catalyst component (C), and in some cases the physical properties of the polymer to be hydrogenated will be affected. Get out.

The catalyst component (D) is added in a molar ratio of (D) / (B) to 0.0 with respect to the catalyst of the catalyst component (B).
In the range of 5 to 10, the hydrogenation activity is high, and the storage stability and the hydrogenation activity persistence are extremely high. The catalyst may be added in an amount of 0.002 to 20 mmol per 100 g of the product to be hydrogenated. 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. 20
Although the hydrogenation reaction is possible even when the amount exceeds the millimolar amount, use of an excessive amount of catalyst becomes uneconomical and disadvantageous in that catalyst deashing and removal after the hydrogenation reaction become complicated. Also,
The preferred catalyst loading for quantitatively hydrogenating the unsaturated double bonds of the conjugated diene units of the polymer under the selected conditions is 0.01 to 5 mmol per 100 g of polymer.

The hydrogenation reaction of the present invention is carried out using molecular hydrogen, and more preferably, it is introduced in the form of gas into the substance to be hydrogenated. 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 hydrogenation rate of the catalyst becomes slow and a large amount of the catalyst is required, which is not economical.
If the temperature exceeds the above range, side reactions, decomposition and gelation are likely to occur simultaneously, and unnecessary hydrogenation of aromatic moieties may occur, which is not preferable. A more preferred temperature range is 20 to 12
It is in the range of 0 ° C.

The pressure of hydrogen used in the hydrogenation reaction is 1 to 1
00 Kg / cm ² is suitable. If it is less than 1 Kg / cm ^2, it is difficult to raise the hydrogenation rate because the hydrogenation rate slows down and the level is virtually reached. If the pressure exceeds 100 Kg / cm ² , the hydrogenation reaction is almost completed at the same time as the pressurization. Is meaningless and causes unnecessary side reactions and gelation, which is not preferable. More preferable hydrogenated hydrogen pressure is 2 to 30 kg / c
Although it is m ² , the optimum hydrogen pressure is selected in consideration of the catalyst addition amount 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 becomes smaller.

The hydrogenation reaction time of the present invention is not limited as it varies depending on the desired hydrogenation rate, but is usually several seconds to 5 seconds.
0 hours. According to the method of the present invention, the olefinically unsaturated double bond in the conjugated diene-based copolymer and the copolymer of the conjugated diene and the vinyl aromatic hydrocarbon is 50% or more, preferably 70% or more, more preferably 80%. % Or more is hydrogenated.

From the solution obtained by carrying out the hydrogenation reaction using the catalyst of the present invention, the hydrogenated target substance can be separated by a chemical or physical means such as precipitation or removal of the heating solvent. 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.
If necessary, the catalyst residue may be removed from the hydrogenated polymer solution to isolate the hydrogenated polymer from the solution.

The hydrogenation method of the present invention is characterized in that the amount of 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 is maintained as compared with the conventional product.

[0064]

EXAMPLES The present invention will now be described in detail with reference to examples, but the present invention is not limited thereto. The hydrogenation rate is ¹ H- before and after hydrogenation of the polymer to be hydrogenated.
Comparing the NMR spectra, based on the phenyl group,
It was determined from the ratio of the reduction amount of olefinically unsaturated double bonds. The following are examples of reagents, catalysts, and polymers used for carrying out the examples.

<Production Example 1: Synthesis of bis (η ⁵ -cyclopentadienyl) titanium di- (p-tolyl)> Anhydrous ether was added to a 1 liter three-necked flask equipped with a stirrer, a dropping funnel and a reflux condenser. 200 ml was added. The apparatus was dried with dry helium, 17.4 g (2.5 mol) of a small piece of lithium wire was cut into a flask, and a solution of 300 ml of ether and 171 g (1 mol) of p-bromotoluene was added dropwise at room temperature and then refluxed. The whole amount of ether solution of p-bromotoluene was gradually added below.

After completion of the reaction, the reaction solution was filtered under a helium atmosphere to obtain a colorless transparent p-tolyllithium solution.
Stirrer replaced with dry helium, 2 liter three neck flask equipped with dropping funnel, bis (cyclopentadienyl)
99.6 g (0.4 mol) of titanium dichloride 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. The residue was dissolved in a small amount of dichloromethane, and 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) di- (p-tolyl) titanium. The yield was 87%. The obtained crystals are orange-yellow needles, have good solubility in toluene and cyclohexane, and have a melting point of 145.
C, elemental analysis value: C = 80.0, H = 6.7, Ti = 1
It was 3.3.

Next, a synthetic example of a conjugated diene-vinyl aromatic hydrocarbon copolymer used for hydrogenation will be shown. <Production Example 2: Synthesis of styrene-isoprene-styrene block copolymer> 1800 g of cyclohexane, 30 g of styrene monomer and n- in a 5 liter autoclave.
Butyllithium (0.32 g) was added, the mixture was polymerized at 60 ° C. for 1 hour, and then 140 g of isoprene monomer was added,
Polymerization was carried out at 0 ° C for 1 hour. Finally, 30 g of styrene monomer was added and polymerization was carried out at 60 ° C. for 1 hour. Of methanol was added to equivalent to the living polymer solution was quenched, after was further precipitated in a large amount of methanol, 1 N H ₂ SO
_After adding ₄ cc and completely decalcifying and washing with methanol, it was vacuum dried at 60 ° C. for 50 hours.

The ¹ H-NMR spectrum of this styrene-isoprene-styrene block copolymer is shown in FIG.
(Enlarged view of the vicinity of 7.5 ppm). 7.4 to 6.
The signal of 5H of phenyl group at 2ppm, the signal of 1H of 1,4 bond at 4.9 to 5.3ppm,
A signal corresponding to 2H of 3,4 bonds is observed at 4.6 to 4.9 ppm. From the signal intensity of the protons of the phenyl group and the olefinically unsaturated double bond, the amount of bound styrene was 30%, and the microstructure of the isoprene part was 1,4, respectively.
The binding was calculated to be 93%, 3,4 binding 7%, 1,2 binding 0%.

The molecular weight was calculated to be 47,000 as the number average molecular weight in terms of polystyrene by the GPC method. <Production Example 3: Synthesis of styrene-butadiene-styrene block copolymer> 1800 g of cyclohexane, 67.5 g of styrene monomer and 0.5 g of n-butyllithium were added to a 5 liter autoclave, and the mixture was polymerized at 60 ° C for 1 hour. Then, 315 g of 1.3-butadiene monomer was added and the mixture was polymerized at 60 ° C. for 1 hour. Finally, 67.5 g of styrene monomer was added, and polymerization was carried out in the same manner as in Production Example 2 except that polymerization was carried out at 60 ° C. for 1 hour.

The polymer obtained has a bound styrene content of 30.
% By weight, block styrene content 28% by weight, the microstructure of the butadiene unit is 1, 2 bonds 12%, 1,
It was calculated to be 88% for 4 bonds. It was a styrene-butadiene-styrene block copolymer having a number average molecular weight of about 60,000 by GPC method.

[0071]

Example 1 The polymer shown in Production Example 2 was dissolved in purified and dried cyclohexane to prepare a polymer concentration of 15% by weight. 40 g of this polymer solution was charged into a 250 ml pressure-resistant metal bottle container, which was dried and replaced with nitrogen. This was degassed under reduced pressure, replaced with hydrogen, and kept at 30 ° C. with stirring. Then, bis (η ⁵ -cyclopentadienyl) titanium di- (p-tolyl) synthesized in Production Example 1 was used as the catalyst component (A), 5 ml of a cyclohexane solution containing 0.25 mmol of this and the catalyst component (B). dibutyl magnesium as) [Mg (n-C ₄ H
₉ ) ₂ ] and a cyclohexane solution containing (B) /
(A) Prepared at a molar ratio of 0.5.

Next, 1,2 polybutadiene (produced by Nippon Soda Co., Ltd., liquid 1,2 polybutadiene, trade name: Nisso B-1000, 1,2 bond content = 85% or less as a catalyst component (C). , Polymer A) 0.5 g, and a cyclohexane solution of n-butanol as a catalyst component (D) was added so that the molar ratio (D) / (B) was 1.0, to prepare a catalyst solution. did.

The whole amount was charged into a pressure resistant metal bottle, and 10.
0 kg / cm²Of dry gaseous hydrogen under stirring
Hydrogenation reaction was carried out at 65 ° C. for 3 hours. Room temperature and pressure
And extract it from the pressure resistant metal bottle, and
Polymer to precipitate, filtered off and dried to give white water.
An addition polymer was obtained. The method of calculating the hydrogenation rate is before and after hydrogenation. ¹
H-NMR spectra are compared and based on the phenyl group
Calculated from the ratio of reduction of unsaturated double bond of conjugated diene
Was. The hydrogenation rate of the obtained hydrogenated polymer is shown in Table 1. Implementation
Of the polymer obtained according to Example 1¹H-NMR spectrum
Is shown in FIG. 2 (enlarged view around 4.5 to 7.5 ppm).

[0074]

Example 2 (B) / (A) molar ratio = 0.56, (D)
The same procedure as in Example 1 was repeated except that the molar ratio of / (B) was changed to 0.77. The experimental conditions and hydrogenation rate are also shown in Table 1.

[0075]

Example 3 (B) / (A) molar ratio = 0.63, (D)
/ (B) molar ratio = 0.60, and the component (B) contains Mg (n-).
Using 0.126 mmol of C ₄ H ₉ ) ₂ and 0.032 mmol of triethylaluminum [Al (C ₂ H ₅ ) ₃ ],
In addition, Example 1 was used except that 1,2 polybutadiene (trade name: B-700, manufactured by Nippon Petrochemical Co., Ltd., 1,2 vinyl bond amount = 57%: hereinafter, polymer B) was used as the catalyst component (C). I went the same way. The experimental conditions and hydrogenation rate are also shown in Table 1.

[0076]

Example 4 Example 1 was repeated except that n-heptanol was used as the component (D). The experimental conditions and hydrogenation rate are also shown in Table 1.

[0077]

[Table 1]

[0078]

Comparative Example 1 (B) / (A) Molar Ratio = 6, (D) /
(B) The same procedure as in Example 1 was repeated except that the molar ratio was changed to 12. For the experimental conditions and hydrogenation rate, see Table 2 as well.
Shown in

[0079]

Comparative Example 2 (B) / (A) Molar Ratio = 6, (D) /
(B) molar ratio = 0.5 and _{varied, Mg (n-C 4 H} 9) 1.
Example 3 was repeated except that 2 mmol and Al (C ₂ H ₅ ) ₃ 0.3 mmol (B) were used. The experimental conditions and hydrogenation rate are also shown in Table 2.

[0080]

Comparative Example 3 (B) / (A) Molar Ratio = 1, (D) /
Example 4 was carried out in the same manner as in Example 4 except that the molar ratio of (B) was changed to 0.5 and n-butyllithium [n-BuLi] was used as the component (B). For experimental conditions and hydrogenation rate,
Similarly, shown in Table 2.

[0081]

[Table 2]

[0082]

Example 5 Mg (n-C) as the catalyst component (B)_FourH₉)
₂0.112 mmol and Al (C ₂H_Five)₃0.02
Example 2 was repeated except that 8 mmol was used. Real
Table 3 shows the test conditions and hydrogenation rate.

[0083]

Comparative Example 4 Except that the catalyst component (C) was not added,
The same procedure as in Example 1 was performed. Table 3 shows the experimental conditions and the hydrogenation rate.

[0084]

[Comparative Example 5] Except that the catalyst component (C) was not added,
The same procedure as in Example 5 was performed. Table 3 shows the experimental conditions and the hydrogenation rate.

[0085]

Reference Example 1 The same procedure as in Example 1 was carried out except that the polymer shown in Production Example 3 was used. Table 3 shows the experimental conditions and the hydrogenation rate.

[0086]

[Table 3]

[0087]

Example 6 The same catalyst mixture as used in Example 1 was stored as it was at room temperature for 1 week in a hydrogen atmosphere.
This stored catalyst solution was subjected to hydrogenation reaction under the same polymer conditions as in Example 1. The results are shown in Table 4, respectively.

[0088]

Example 7 The same catalyst mixture as that used in Example 1 was stored in a hydrogen atmosphere for 2 weeks at room temperature.
This stored catalyst solution was subjected to hydrogenation reaction under the same polymer conditions as in Example 1. The results are shown in Table 4, respectively.

[0089]

COMPARATIVE EXAMPLE 6 The catalyst solution used in Example 1, in which n-butanol was not added, was stored in a hydrogen atmosphere for 2 weeks at room temperature. This stored catalyst solution was subjected to hydrogenation reaction under the same polymer conditions as in Example 3. The results are shown in Table 4, respectively.

[0090]

[Table 4]

[0091]

As described above, according to the method of the present invention, a method for hydrogenating an alkyl group-substituted olefinically unsaturated double bond can be efficiently performed. In particular, a conjugated diene-based polymer having an olefinically unsaturated double bond having an alkyl substituent other than the main chain, or a conjugated diene having an olefinically unsaturated double bond having an alkyl substituent other than the main chain and a vinyl aromatic carbon When the conjugated diene part of the copolymer with hydrogen is isoprene, most of the 1,4 bonds are hydrogenated in this type of catalyst because of the steric hindrance of the unsaturated double bond part of the 1,4 bonds of isoprene. I couldn't do it. However, according to the method of the present invention, it becomes possible to highly selectively hydrogenate these polymers at a high level under mild conditions. In addition, the long-term storage stability of the catalyst is increased, and it is less affected by the catalyst preparation state and impurities in the system, which obviates the trouble of preparing the catalyst immediately before hydrogenation and also rationalizes the process. Further, the hydrogenated polymer obtained by the method of the present invention is used as an elastic body having excellent weather resistance and oxidation resistance, a thermoplastic elastic body or a thermoplastic resin, and also an ultraviolet absorber, an oil, a filler, etc. It is extremely useful industrially because it is used by adding additives or blending with other elastic materials and resins.

[Brief description of drawings]

FIG. 1 Styrene-isoprene of Production Example 2 before hydrogenation
-Of styrene block copolymer ¹H-NMR spectrum
(4.5 to 7.5 ppm).

FIG. 2 Styrene-hydrogenated isoprene hydrogenated in Example 1
-Of styrene block copolymer ¹H-NMR spectrum
(4.5 to 7.5 ppm).

Claims (3)

[Claims] 1. A monomer unit constituting a polymer chain,
A conjugated diene polymer in which one or two of two carbons having an olefinically unsaturated double bond are substituted with a C _{1 to} C ₈ alkyl group, or a monomer unit constituting a polymer chain And a copolymer of a conjugated diene in which one or two of two carbons having an olefinically unsaturated double bond are substituted with a C _{1 to} C ₈ alkyl group and a vinyl aromatic hydrocarbon, In a method of hydrogenating an olefinically unsaturated double bond of the polymer by bringing it into contact with hydrogen in an inert organic solvent, it is composed of the following components (A) to (D),
A catalyst composition prepared by reducing (A) with (B) and then adding (D) in the presence of (C) (however, component (B) / component (A) (molar ratio) = 0.05). To 5, and (D) component / (B) component (molar ratio) = 0.05 to 10) are used, the hydrogenation method of the alkyl group substituted conjugated diene polymer characterized by the above-mentioned. (A) At least one titanocene compound represented by the following formula (1): (However, R ¹ and R ² represent a group selected from a C _{1 to} C ₁₂ hydrocarbon group, an aryloxy group, an alkoxy group, a halogen group, and a carbonyl group, and R ¹ and R ² may be the same or different. Cp represents a cyclopentadienyl ring.) (B) At least one reducing agent selected from an organic Mg compound, an organic Zn compound, and an organic Al compound having a reducing ability. (C) Olefinically unsaturated side chain. Olefinically unsaturated double bond-containing polymer having a number average molecular weight of 500 or more and 10000 or less, in which the ratio of double bonds to the total amount of olefinically unsaturated double bonds is 0.3 to 1 (D) The following (2) An alcohol represented by the formula (provided that R ³
Represents a C _{1 to} C ₂₀ hydrocarbon group) 2. The catalyst composition prepared in advance in a catalyst tank,
The method for hydrogenating an alkyl group-substituted conjugated diene polymer according to claim 1, wherein the hydrogenation reaction is carried out by transferring this to a hydrogenation tank. 3. A monomer unit constituting a polymer chain, one of two carbons having an olefinically unsaturated double bond.
One or two of the two carbons having an olefinically unsaturated double bond, which is a conjugated diene polymer in which one or two are substituted with a C1 to C8 alkyl group, or a monomer unit constituting a polymer chain. Or 2 are monomer units constituting a polymer chain of a copolymer of a conjugated diene substituted with a C _{1 to} C ₈ alkyl group and a vinyl aromatic hydrocarbon, and an olefinically unsaturated double bond The water of the alkyl group-substituted conjugated diene polymer according to claim 1 or 2, wherein the conjugated diene moiety in which one or two of the two carbons having is substituted with a C _{1 to} C ₈ alkyl group is isoprene. How to add.