JPH0496905A - Hydrogenation of olefinic compound - Google Patents

Abstract

PURPOSE:To selectively hydrogenate the subject compound with hydrogen in an organic solvent in the presence of a long term stable catalyst consisting of a specific metallocene compound and a metal compound having reducibility in the coexistence of a side chain double bond-containing polymer. CONSTITUTION:In a method for hydrogenating the olefinic unsaturated double bond of an olefinic unsaturated double bond-containing compound with hydrogen in an organic solvent in the presence of a catalyst consisting of (A) at least one of metallocene compounds of the formula (R<1>, R<2> are 1-12C hydrocarbon, aryloxy, alkoxy, halogen, carbonyl; M is Ti, Zr, Hf) and (B) at least one of Li, Na, K, Al, Zn or Mg-containing compounds having reducibility, (C) an olefinic unsaturated double bond-containing polymer having a ratio of (0.3-1):1 between the content of the olefinic unsaturated double bonds on the side chains and the content of all olefinic unsaturated double bonds of the polymer is added to the hydrogenation reaction system.

Description

Detailed Description of the Invention [Industrial Field of Application] The present invention relates to a hydrogenation method capable of selectively hydrogenating olefinically unsaturated double bonds in a compound containing olefinically unsaturated double bonds. .

[Conventional technology]

Heterogeneous catalysts and homogeneous catalysts are generally known as hydrogenation catalysts for compounds having olefinically unsaturated double bonds. The former type of heterogeneous catalyst is widely used industrially, but it generally has lower activity than homogeneous catalysts, requires a large amount of catalyst to carry out the desired hydrogenation reaction, and cannot be carried out at high temperature and pressure. This makes it uneconomical. On the other hand, the latter type of homogeneous catalyst usually progresses the hydrogenation reaction in a homogeneous system, so compared to a heterogeneous system, it is highly active and requires less catalyst usage, and can be hydrogenated at lower temperatures and pressures. On the other hand, catalyst preparation is complicated, the stability of the catalyst itself is not sufficient, the reproducibility is poor, and undesirable side reactions are likely to occur. Therefore, there is currently a strong desire to develop a hydrogenation catalyst that is highly active and easy to handle.

On the other hand, in polymers containing olefinic unsaturated double bonds, while the unsaturated double bonds are advantageously used for vulcanization, etc., such double bonds have poor stability such as weather resistance and oxidation resistance. It has its drawbacks. These disadvantages of poor stability can be significantly improved by hydrogenating the polymer to eliminate unsaturated double bonds in the polymer chain. However, when hydrogenating a polymer, compared to when hydrogenating a low-molecular compound, hydrogenation becomes difficult due to the influence of the viscosity of the reaction system, steric hindrance of the polymer chain, etc. Furthermore, it is extremely difficult to physically remove the catalyst after hydrogenation, and it is virtually impossible to completely separate it.
There are some drawbacks such as. Therefore, in order to hydrogenate polymers in a manner similar to Economics 11'J, it is necessary to use a high-talk hydrogenation catalyst that exhibits activity with a moderate amount of deashing, or a highly talkative hydrogenation catalyst that is extremely easy to deash. There is a strong desire to develop a catalyst that can

The present inventors have already developed a method for hydrogenating olefin compounds by combining a specific titanocene compound and alkyl lithium (JP-A-61-33132, JP-B-1-53851).
No.>, metallocene compounds and organic aluminum, zinc,
Olefinically unsaturated (co-) in combination with magnesium
Method of hydrogenating polymers (JP-A-6L-28507Q, 6
2-209102, 62-209103), a method of hydrogenating an olefinically unsaturated group-containing living polymer by combining a specific titanocene compound and an alkyl lithium (JP-A No. 61-47706, JP-B No. 63-54)
No. 02) etc. have already been invented.

However, these methods require difficult handling of the hydrogenation catalyst.
Long-term storage stability is also difficult, and a method that can further reduce the amount of catalyst has been desired.

[Problems to be solved by the present invention]

The purpose of the present invention is to discover a highly active hydrogenation catalyst that is stable, easy to handle, can withstand long-term storage, and exhibits reproducible activity in extremely small amounts used in hydrogenation reactions, and in particular can be used in the hydrogenation of polymers without the need for deashing. The problem to be solved is to invent a highly active hydrogenation catalyst that exhibits activity in a small amount of usage, and to find a method to obtain hydrogenated polymers with excellent weather resistance, oxidation resistance, and ozone resistance. It is something that exists.

[Means and effects for solving the problems] The present invention provides that when reducing a metallocene compound with a lithium-, sodium-, potassium-, aluminum-, zinc- or magnesium-containing compound having a reducing ability, a specific proportion or more of an olefinic impurity is added to the side chain. Hydrogenation catalysts made of coexisting polymers with saturated double bonds have extremely high storage stability.
It exhibits extremely high hydrogenation activity for olefinically unsaturated double bonds under mild conditions with good reproducibility, and can remove unsaturated double bonds from polymers containing olefinically unsaturated double bonds without the need for deashing. This was based on the surprising fact that hydrogenation can be selectively carried out in a moderate amount and under mild conditions.

That is, the present invention provides a method for hydrogenating the olefinically unsaturated double bonds in the compound by contacting the olefinically unsaturated double bond Kinsen compound with hydrogen in an inert solvent. A) At least one metallocene compound represented by the following general formula (wherein R' and R2 represent a group selected from a C1 to C12 hydrocarbon group, an aryloxy group, an alkoxy group, a halogen group, and a carbonyl group, and R1 , R2 may be the same or different.

Further, M represents a metal selected from any one of r*, zr, and 1-u. ) (B) Lithium, sodium having jW element capacity,
(C) When reducing at least one of potassium, aluminum, zinc or magnesium dowel compounds, (C) the fraction of olefinically unsaturated double bonds in the side chain relative to the total amount of olefinically unsaturated double bonds is 0;゜3
This invention relates to a method for hydrogenating an olefinically unsaturated double bond-containing compound, characterized in that the catalyst for the hydrogenation is a coexisting olefinically unsaturated double bond-containing gold polymer of 1 to 1. .

A method of hydrogenating an olefinically unsaturated double bond in an olefinically unsaturated double bond gold polymer by combining at least one type of general formula (A) and a compound (B) having reducing power according to the present invention has already been filed by the present inventors (Japanese Patent Application Laid-Open No. 61-28507, Japanese Patent Application Laid-open No. 1-016)
No. 401).

As a result of further intensive study by the present inventors on a method for hydrogenating olefins efficiently and economically with excellent storage stability and good reproducibility by further improving the activity of this prior application's olefin hydrogenation catalyst system, When reducing such metallocene compounds with lithium, sodium, potassium, aluminum, zinc or magnesium compounds that have reducing power, from those in which a polymer having a specific proportion or more of olefinically unsaturated double bonds in the side chain coexists. The present invention was completed based on the discovery that a hydrogenation catalyst of the present invention has further improved hydrogenation activity, excellent long-term storage stability, and excellent reproducibility when compared to a hydrogenation catalyst without the coexistence of the polymer. .

The olefin compound hydrogenation catalyst component (A) according to the present invention has the general formula R2 and R3 may be the same or different. M represents a metal selected from Ti, Zr, and Hf.) The C1 to C1° hydrocarbon groups of R and R include For example, substituents such as (wherein R3-R5 represent hydrogen or a C-C alkyl hydrocarbon group, one or more of R3-R5 is hydrogen, and n=0 or 1) are also included. R
If all 3-R5s are alkyl groups, it is difficult to synthesize with good yield due to steric hindrance, which is not preferred.

Furthermore, compounds in which the alkyl hydrocarbon group is ortho to the central metal are difficult to synthesize.

Specific examples of such catalysts (A) include bis(cyclopentajenyl)titanium dimethyl, bis(cyclopentajenyl)titanium diethyl, bis(cyclopentagenyl)titanium diethyl, bis(cyclopentagenyl) Titanium di-5ec-butyl, bis(cyclopentadienyl) titanium diethyl, bis(cyclope>tanenyl) titanium dioctyl, bis(cyclopentadienyl) titanium jetoxide, bis(cyclopentagenyl) titanium jetoxide, bis(cyclo pentagenyl) titanium jetoxide, bis(
cyclopentagenyl) titanium diphenyl, bis(
cyclopentagenyl) titanium di-m-tolyl, bis(cyclopentagenyl) titanium di-p-tolyl, bis(cyclopentagenyl) titanium di-m-tolyl, bis(cyclopentagenyl) titanium di-4
-ethylphenyl, bis(cyclopentagenyl) titanium di-4-butylphenyl, bis(cyclopentagenyl) titanium di-4-hexylphenyl, bis(
cyclopentagenyl) titanium diphenoxide, bis(cyclopentagenyl) titanium dichloride,
Bis(cyclopentagenyl) titanium dichloride, bis(cyclopentagenyl) titanium dichloride, bis(cyclopentagenyl) titanium dioctyl, bis(cyclopentagenyl) titanium diorphonyl, bis(cyclopentagenyl) titanium Methyl chloride, Bis(cyclopentagenyl) titanium chloride ethoxide, Bis(cyclopentagenyl) titanium chloride phenoxyto, Bis(cyclopentagenyl) titanium dibenzyl, Bis(cyclopentagenyl) zirconium dimethyl, Bis( cyclopentagenyl) zirconium diethyl, bis(cyclopentagenyl) zirconium-n-butyl, bis(cyclopentagenyl) zirconium di-5ee-butyl,
bis(cyclopentadienyl)zirconium diethyl,
Bis(cyclopentagenyl)zirconium dioctyl, bis(cyclopentagenyl)zirconium jetoxide, bis(cyclopentagenyl)zirconium jetoxide, bis(cyclopentagenyl)zirconium jetoxide, bis(cyclopentagenyl) Zirconium diphenyl, bis(cyclopentadienyl) zirconium di-m-tolyl, bis(cyclopentadienyl)
Zirconium p-tolyl, bis(cyclopentadienyl)zirconium-m,p-xylyl, bis(cyclopentagenyl)zirconium di-4ethyl phenyl,
Bis(cyclopentagenyl)zirconium diphenoxide, bis(cyclopentagenyl)zirconium dichloride, bis(cyclopentagenyl)zirconium dichloride, bis(cyclopentagenyl)zirconium dichloride, bis(cyclopentagenyl)zirconium dioctyl , bis(cyclopentagenyl) zirconium dicarbonyl, bis(cyclopentagenyl) zirconium chloride methyl, bis(cyclopentagenyl) hafnium dimethyl, bis(cyclopentagenyl) hafnium diethyl, bis(cyclopentagenyl) hafnium di-n-butyl, bis(cyclopentagenyl) hafnium di-5ec-butyl, bis(cyclopentagenyl) dihexyl, bis(cyclopentagenyl) hafnium jetoxide, bis(cyclopentagenyl) hafnium jetoxide, bis(cyclopentadienyl)no\fnium dibutokind, bis(cyclopentadienyl)nophnium diphenyl, bis(cyclopentagenyl)hafnium di-m-tolyl, bis(
cyclopentagenyl) hafnium di-p-tolyl, bis(cyclopentagenyl) hafnium di-m, p-
Xylyl, bis(cyclopentagenyl)no1phnium diphenoxide, bis(cyclopentagenyl) hafnium dichloride, bis(cyclopentagenyl) hafnium dichloride, bis(cyclopentagenyl) hafnium dichloride, bis(cyclopentagenyl) hafnium dichloride pentagenyl)
hafnium dichloride, bis(cyclopentagenyl)no1phnium dicarbonyl, bis(cyclopentagenyl) hafnium chloride methyl, bis(pentamethylcyclopentagenyl) titanium dimethyl, bis(
pentamethylcyclopentagenyl) titanium diphenyl, bis(pentamethylcyclopentagenyl) titanium di-m-)lyl, bis(pentamethylcyclopentagenyl) titanium di-p-tolyl, bis(pentamethylcyclopentagenyl) titanium di-p-tolyl ) titanium dichloride, etc. These can be used alone or in combination with each other. Among these metallocene compounds, preferred ones have high hydrogenation activity for olefinically unsaturated double bonds in olefin compounds and can selectively hydrogenate unsaturated double bonds under mild conditions.
Bis(cyclopentagenyl) titanium dimethyl, bis(cyclopentagenyl) titanium di-n-butyl, bis(cyclopentagenyl) titanium dichloride, bis(cyclopentagenyl) titanium diphenyl, bis(cyclopentagenyl) titanium dichloride ) titanium di-p-
Tolyl, bis(cyclopentagenyl) titanium dicarbonyl, bis(cyclopentagenyl) hafnium dichloride, bis(cyclopentagenyl) hafnium dichloride, bis(cyclopentagenyl) hafnium diphenyl, bis(cyclopentagenyl) hafnium di-p-tolyl, bis(cyclopentagenyl) hafnium p-lyl, bis(cyclopentagenyl)zirconium dimethyl, bis(cyclopentagenyl)zirconium di-n-butyl, bis(cyclopentagenyl) ) Zirconium dichloride, bis(nclopestadienyl) zirconium dichloride, bis(cyclopentadienyl) zirconium diphenyl, bis(cyclopentadienyl) zirconium di-p-tolyl, bis(cyclopentadienyl) zirconium dicarbonyl It will be done. More preferred are bis(cyclopentagenyl)titanium dichloride, which can be handled stably and exhibits the most activity when combined with the reducing metal compound (B), and bis(cyclopentagenyl)titanium di- Tolyl is the most preferred, with the latter having excellent solubility.

On the other hand, the catalyst component (B) is an organometallic compound capable of reducing the metallocene compound of the catalyst component (A), such as an organolithium compound, an organoaluminum compound, an organozinc compound, an organomagnesium compound, an organic sodium compound, The polymer can be hydrogenated by using an organic potassium compound or the like alone or in combination with each other.

Examples of organolithium compounds include the general formula R7-Li[
However, R7 is a c-c hydrocarbon group, an aryloxy group, or an alkoxy group, and the 01 to C1 degree hydrocarbon group is (however, R3-R5 represents hydrogen or a C-c alkyl hydrocarbon group, and R3- One or more of R5 is hydrogen and n=0 or 1). ] are preferably used, and specific examples include methyllithium, ethyllithium, n-propyllithium, isopropyllithium, n-butyllithium, 5ee
-butyllithium, isobutyllithium, n-pentyllithium, n-hexyllithium, phenyllithium,
m-tolyllithium, p-t-lyllithium, xylyllithium, me) xylithium, ethoxylithium, n
-propoquine lithium, isopropoquine lithium, n-
Butoxylithium, 5ec-butoxylithium, t-butoxylithium, pentyloxylithium, hensyloxylithium, octyloxylithium, phenoxylithium, 4-methylphenoxylithium, hensyloxylithium, 4-methylbenzyloxylithium, etc. It will be done.

Lithium phenolate compounds obtained by reacting phenolic stabilizers with alkyl lithiums are also used. Specific examples of such phenolic stabilizers include 1-
Oxy-3-methyl-4-isopropylbenzene, 2
, 6-tert-butylphenol, 2,6-tert-butyl-4-ethylphenol, 2,6-tert-butyl-p-cresol, 2,6-tert-butyl-p-cresol, 2,6-tert-butyl-4-ethylphenol, 2,6-tert-butyl-p-cresol
ert-butyl-4-n-butylphenol, 4-hydroxymethyl-2,6-tert-butylphenol, butylhydroxyanisole, 2-(1-methylcyclohexyl)-4,6-dimethylphenol, 2.
4-dimethyl-6tert-butylphenol, 2-methyl-4,6-ditunylphenol, 2.6-tert-butylphenol
rt-butyl-α dimethylamino-p=cresol, methylene-bis(dimethyl-4,6-phenol), 2,
2'-methylene-bis-(4-methyl-6-ter
t-butylphenol), 2,2'-methylene-bis-(4methyl-6-chlorohexylphenol),
2.2'-methylene-bis-(4-ethyl-6te
rt~butylphenol), 4,4'-methylenebis-(2,6-tert-butylphenol), 2
．． Examples include 2'-methylene-bis-(6-α-methyl-benzyl-p-cresol).

2,6-tert-butyl-p-cresol, the most widely used 2,6-tert-butyl-p-cresol, has a hydroxyl group of 10 Li.
-Butyl-4-methylphenoxylithium is particularly preferably used.

Furthermore, organosilicon lithium compounds such as trimethylsilyllithium, dimethylethylsilyllithium/dimethylethylsilyllithium, trimethylsilylsilyllithium, diethylmethylsiloxylithium, triethylsiloxylithium, and triphenylsilyllithium may be used.

As an aluminum compound, trimethylaluminum,
Triethylaluminum, triisobutylaluminum, triphenylaluminum, diethylaluminium chloride, ethylaluminum dichloride, methylaluminum sesquichloride, ethylaluminum sesquichloride, diethylaluminum hydride, diisobutylaluminum hydride, triphenylaluminum, tri(2-ethylhexyl)aluminum, methyl Examples of zinc compounds include diethylzinc, bis(cyclopentadienyl)zinc, diphenylzinc, etc., and magnesium compounds include diethylmagnesium, diethylmagnesium, methylmagnesium bromide, and ethylmac'. Examples include magnesium chloride, ethylmagnesium bromide, ethylmagnesium chloride, phenylmagnesium bromide, phenylmagnesium chloride, dibutylmagnesium, and t-butylmagnesium chloride. Furthermore, sodium compounds include methyl sodium, ethyl sodium, n-propyl sodium, isopropyl sodium, n-butyl sodium, see-butyl sodium, isobutyl sodium, n-pentyl sodium, n-hexyl sodium, hensyl sodium, phenyl sodium, and triphenyl sodium. Methyl sodium, sodium naphthalene, hexynyl sodium, phenylethyl sodium, cyclopentadienyl sodium, pentamethylclopentadienyl sodium, triethylaluminum, triphenylsilyl sodium, etc., and potassium compounds include methylpotassium, ethylpotassium, Examples include triphenylmethylpotassium and phenylethylpotassium. In addition to these, sodium aluminum hydride, lithium aluminum hydride, diisobutyl sodium aluminum hydride, tri(t-butoxy) lithium aluminum hydride, triethyl sodium aluminum hydride, diisobutyl sodium aluminum hydride, isobutyl sodium aluminum hydride, triethyl sodium aluminum hydride, triethoxy sodium A reducing agent containing two or more metals such as aluminum hydride and triethyllithium aluminum hydride may also be used.

These may be used in combination of two or more types, or may be a mutual complex of two or more types. n-butyllithium is most preferred because it exhibits the highest hydrogenation activity and selectively hydrogenates olefinically unsaturated double bonds.

The ratio of the amount of olefinically unsaturated double bonds in the side chain of component (C) to the total amount of olefinically unsaturated double bonds is 0.
Examples of monomers used in the preparation of polymers with an olefinically unsaturated double bond density of 3 to 1 include conjugated dienes, generally conjugated dienes having from 4 to about 12 carbon atoms. .

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, and the like. These may be used alone or in combination of two or more. Particularly preferred are 1,3-butadiene and isoprene, which can be industrially advantageously developed and are relatively easy to handle, and polybutadiene, polyisoprene, and butadiene/isoprene copolymers are preferred. Also, norbornadiene, dicyclopentadiene, 2
, 3-dihydrodicyclopentadiene and their alkyl substituted products may be used alone or as a copolymer.

The polymer of component (C) may have a number average molecular weight of 500 or more, and the upper limit of the molecular weight may be any value.

If the number average molecular weight is less than 500, the stabilizing effect will be small, so a liquid rubber with a number average molecular weight of 500 or more is preferred because it is easy to handle.

Liquid rubber is liquid at room temperature or has a number average molecular weight of 50.
It should be between 0 and 10,000.

When the number average molecular weight exceeds 10,000, there is no particular problem in terms of performance, except that handling as a liquid becomes difficult. Microstructure is important in such polymers. That is, "the fraction of olefinically unsaturated double bonds in the side chain to the total olefinically unsaturated double bonds" is defined as follows.

It is essential that this value is between 0.3 and 1, but within this range it may have a functional group such as a hydroxyl group, carboxyl group, or amino group at the end.

To give a specific example, in the case of polybutadiene, there are 30 to 100 1,2-vinyl bonds for all olefinically unsaturated double bonds (cis 1,4 bonds, trans 1,4 bonds, 1,2-vinyl bonds). % is necessary. In addition, in the case of polyisoprene, all olefinically unsaturated double bonds (cis 1,4 bonds, trans 1,4 bonds, 1,2 bonds, 3,4
bond), and the side chain olefinically unsaturated double bond (1
, 2 bonds + 3,4 bonds) should be in the range of 30 to 100%. If this ratio is less than 0.3, the hydrogenation catalyst becomes unstable and difficult to handle, has poor storage stability, and may cause problems in reproducibility if not handled properly.

The polymer may also be a copolymer of a conjugated diene aromatic vinyl compound. Specific examples of aromatic vinyl compounds include styrene, t-butylstyrene, α-methylstyrene, and p-methylstyrene.
Examples include -methylstyrene, divinylbenzene, 1,1-diphenylethylene, N,N-diethyl-p-aminoethylstyrene, N,N-diethyl-p-aminoethylstyrene, and styrene is particularly preferred. As specific examples of copolymers, butadiene/styrene copolymers, isoprene/styrene copolymers, etc. are most preferred.

These copolymers may be random, block, star block, tapered block, etc., and are not particularly limited.
do not have. In addition, the suspension of bonded vinyl compounds is 70%.
If it is less than 1.70 (preferably 1.70), if it exceeds +G, the stability of the conjugated carbon moiety will actually decrease, and the stabilizing effect of the C reduction catalyst will be small. It is necessary that the ratio of saturated double bonds to the total olefinic double bonds be 0.3 to 1.

These catalyst components (C) are used for radical polymerization, cationic polymerization,
Polymerization may be carried out using either anionic polymerization or coordinated anionic polymerization method. In order to increase the amount of olefinically unsaturated double bonds in the side chain, organic It is preferable to obtain it by living anion polymerization using lithium or an organic sulfur compound as a catalyst, by coordinating anion polymerization using a cobalt-based Ziegler type catalyst, or by copolymerizing ethylene and dicyclopentadiene.

Specific examples of such polar solvents include tetrahydrofuran, tetramethylethylenecyamine, trimethylamine, triethylamine, ethyl ether, tetrahydropyran,
Examples include dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and dibiperidinoethane. Methyllithium as a Li-based catalyst,
Ethyllithium, n-propyllithium, isopropyllithium, n-butyllithium, 5ee-butyllithium, isobutyllithium, tert-butyllithium,
Examples include 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 of the present invention can be applied to all compounds having olefinically unsaturated double bonds. For example, it is suitably used for the hydrogenation of 1-butene, 1,3-butadiene, cyclopentene, 1,3-pentadiene, 1-hexene, 2-hexene, 1-methylcyclohexene, styrene, 1-octene, and the like.

On the other hand, since the hydrogenation catalyst of the present invention has high hydrogenation activity and selectivity, it is particularly suitable for hydrogenation of polymers having unsaturated double bonds.

Although the present invention can be applied to all polymers having unsaturated double bonds, preferred embodiments include conjugated diene polymers, copolymers of conjugated dienes and olefin monomers, norhorne polymers, and cyclopentene polymers. etc. In particular, conjugated diene polymers and hydrogenated copolymers of conjugated dienes and olefin monomers are industrially useful as elastic bodies and thermoplastic elastomers.

Conjugated dienes used in the production of such conjugated diene polymers include conjugated dienes having from 4 to about 12 carbon atoms in the membrane, specific examples 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. 1.3-
Butadiene and isoprene are particularly preferred.

Furthermore, as the olefin monomer copolymerizable with at least one conjugated diene, vinyl-substituted aromatic hydrocarbons are particularly preferred. That is, in order to fully exhibit the effect of the present invention of selectively hydrogenating only the unsaturated double bonds of the conjugated diene unit, and to obtain industrially useful and valuable elastic bodies and thermoplastic elastic bodies, it is necessary to Of particular interest are copolymers of dienes and vinyl-substituted aromatic hydrocarbons. Specific examples of vinyl-substituted aromatic hydrocarbons used include styrene, t-butylstyrene, α-methylstyrene, p-methylstyrene, divinylbenzene, 1,1-diphenylethylene, N,N-
Dimethyl-p-aminoethylstyrene, N, N'-
Examples include diethyl-p-aminoethylstyrene, and styrene is particularly preferred. As specific examples of copolymers, butadiene/styrene copolymers, isoprene/styrene copolymers, etc. are most preferred since they provide hydrogenated copolymers with high T-aggregate value.

Among such copolymers, block copolymers provide hydrogenated polymers that are industrially most useful as thermoplastic elastomers, or block copolymers have at least one conjugated diene-based block at the end. is particularly preferably used because it provides a hydrogenated polymer with excellent processability, compatibility with other olefin polymers, adhesive properties, etc., compared to those without a conjugated diene block at the end.

A preferred embodiment of the hydrogenation reaction of the present invention is carried out in a solution in which a compound having an olefinically unsaturated double bond or the above polymer is dissolved in an inert organic solvent. Of course, in the case of low molecular weight compounds that are liquid at room temperature, such as cyclohexene and cyclooctene, the hydrogenation reaction can be carried out without dissolving them in a solvent, but in order to carry out the reaction uniformly and under mild conditions, a solution dissolved in a solvent is required. It is preferable to carry out at "Inert organic solvent" means a solvent that does not react with any participant in the hydrogenation reaction. Suitable solvents include, for example, aliphatic hydrocarbons such as n-pentane, n-hexane, n-hebutane, n-octane, alicyclic hydrocarbons such as cyclohexane, cyclohebutane, diethyl ether, and tetrahydrofuran. It is a single or a mixture of ethers.

Aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene can also be used as long as aromatic double bonds are not hydrogenated under the selected hydrogenation reaction conditions.

In the hydrogenation reaction of the present invention, the hydrogenated product solution is maintained in the membrane at a predetermined temperature under hydrogen or an inert atmosphere, a hydrogenation catalyst is added with or without stirring, and then This is carried out by introducing hydrogen gas and pressurizing it to a predetermined pressure.

An inert atmosphere means an atmosphere that does not react with any participants in the hydrogenation reaction, such as helium, neon, argon, and the like. Air and oxygen are not preferred because they oxidize catalyst components and cause catalyst deactivation. Further, nitrogen is not preferred because it acts as a catalyst poison during the hydrogenation reaction and reduces the hydrogenation activity. In particular, it is most preferable that the inside of the hydrogenation reactor be in an atmosphere containing only hydrogen scum.

On the other hand, the catalyst is made of catalyst components (A) and (B) in advance.
It is preferable to use a mixture of , and (C), or to use a mixture of (A) reduced with (B) in the presence of (C), since they have high activity. In addition to the above-mentioned inert atmosphere, the reducing atmosphere may be hydrogen. The reduction temperature and the storage temperature are between -50°C and 50°C, particularly preferably between -20°C and 30°C.

It is necessary to handle the catalyst component (B) under the above-mentioned inert atmosphere. Although the catalyst component (A) may be stable in air, it is preferable to handle it under an inert atmosphere.

It is preferable to use components (A), (B), and (C) as a solution in the above-mentioned inert organic solvent because it is easier to handle. As the inert organic solvent used when the solution is used, the various solvents mentioned above that do not react with any of the participants in the hydrogenation reaction can be used. Preferably, it is the same solvent as used in the hydrogenation reaction.

When adding catalyst components to the hydrogenation reactor, it is most preferred to do so under a hydrogen atmosphere. The temperature during addition is -30°C to 100°C, preferably =10°C to 50°C.
Preferably, it is prepared immediately before the hydrogenation reaction at a temperature of °C.
If it is stored under a hydrogen atmosphere or an inert atmosphere, it can be used without substantially changing its hydrogenation activity for about two months even at room temperature.

The mixing ratio of each catalyst component to exhibit high hydrogenation activity and hydrogenation selectivity is the ratio of the number of metal moles of catalyst component (B) to the number of moles of catalyst component (A) (hereinafter referred to as "Metal (B)").
/Metal (A) molar ratio) is in the range of about 20 or less. Quantitative hydrogenation reaction can also be carried out at the Metal (B)/Metal (A) molar ratio -0, but it requires higher temperature and pressure conditions, and Metal (B)
) / Metal (A) When the molar ratio exceeds 20, it is not only uneconomical due to excessive use of the expensive catalyst component (B) that does not contribute to substantial improvement in activity, but also tends to cause unnecessary side reactions. Undesirable.

Metal (B) / Metal (A) molar ratio -
The range of 0.5 to 10 is most suitable for significantly improving hydrogenation activity.

In the case of a living polymer obtained by anionic polymerization using a hydrogenated substance, this Metal (B)/Metal
(A) In order to achieve the molar ratio, various active hydrogens and halogens may be deactivated with a compound that 1. Compounds having such 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-pentanol,
Alcohols such as 2-heptal, 3-heptatool, 4-heptatool, ophthal, nonanol, decanol, undecanol, lauryl alcohol, allyl alcohol, cyclohexanol, cyclopentanol, benzyl alcohol, phenol, 0-cresol, m-
Cresol, p-cresol, p-allylphenol,
2.6-di-t-butyl-p-cresol, xylenol, dihydroanthraquinone, dihydroxycoumarin,
Examples include phenols such as 1-hydroxyanthraquinone, m-hydroxybenzyl alcohol, resorcinol, and leukoaralin.

Examples of acids include organic carboxylic acids such as acetic acid, propionic acid, butyric acid, isobutyric acid, pentanoic acid, hexanoic acid, heptanoic acid, decanoic acid, myristic acid, stearic acid, behenic acid, benzoic acid, and methylbenzoic acid. can.

Compounds containing halogen include benzyl chloride, trimethylsilyl chloride (bromide), t-butyl chloride (bromide), methyl chloride (bromide), ethyl chloride (bromide), propyrochloride (bromide), and n-butyl chloride (bromide). etc. can be mentioned. The amount of catalyst component (C) added is 10 to 5 by weight relative to the catalyst component (A).
00 is preferred. If it is smaller than 10, the effects of storage stabilization and catalyst amount reduction will be small.

Hydrogenation activity is good even if it exceeds 500, but when the hydrogenated substance is a polymer, it is difficult to separate the hydrogenated polymer from the catalyst (C) component, so in some cases, the physical properties etc. will be affected.

The hydrogenated product is a polymer containing olefinically unsaturated double bonds, and the olefinically unsaturated double bonds in the side chain are 0.3 -1, E, 1, this '1 part may be used as the (C) catalyst component, or may be used in combination with another (C) component.

The amount of catalyst added is 0.002 to 2 per 100 g of hydrogenated material.
0 mmol is sufficient. If the amount added is within this range, it is possible to preferentially hydrogenate the olefinically unsaturated double bonds of the hydrogenated product, and hydrogenation of the aromatic double bonds in the copolymer does not substantially occur. Therefore, extremely high hydrogenation selectivity is achieved. Is it possible to carry out the hydrogenation reaction even if the amount exceeds 20 mmol, or is it uneconomical to use more catalyst than necessary?
This is disadvantageous, such as complicating catalyst deashing and removal after the hydrogenation reaction.

The preferred amount of catalyst added to quantitatively hydrogenate the unsaturated double bonds of the conjugated diene units of the polymer under 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, more preferably introduced in the form of dregs into the hydrogenate solution.

It is more preferable that the hydrogenation reaction is carried out with stirring, and the introduced hydrogen can be rapidly mixed with the hydrogenated substance. The hydrogenation reaction is generally carried out at a temperature range of 0 to 150°C. If the temperature is less than 0°C, the activity of the catalyst will decrease, and the hydrogenation rate will be slow, requiring a large amount of catalyst, making it uneconomical. If the temperature exceeds 150"C, side reactions, decomposition, and gelation will easily occur. , and hydrogenation of the aromatic nucleus portion also tends to occur, which is undesirable because the hydrogenation selectivity decreases.The temperature is generally preferably in the range of 20 to 120°C.

The pressure of hydrogen used in the hydrogenation reaction is 1 to 100Kl/
' crA is preferred. If the pressure is less than 1 to 9 J/ci, the hydrogenation rate will slow down and virtually reach a plateau, making it difficult to increase the hydrogenation rate. This is not preferable because it is almost complete and has no practical meaning, and it causes unnecessary side reactions and gelation.

A more preferable hydrogenation pressure is 2 to 30'j/cri
Or, it is preferable that the optimum hydrogen pressure is selected in correlation with the amount of catalyst added, etc., and that the hydrogen repulsion force is selected on the high pressure side as the preferable amount of catalyst becomes smaller. Furthermore, since low molecular olefins have a faster hydrogenation rate than polymers, milder conditions are selected than in the case of polymers.

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 selecting other hydrogenation reaction conditions.

From a solution subjected to a hydrogenation reaction using the catalyst of the present invention, the hydrogenated target product can be easily separated by chemical or physical means such as distillation or precipitation.

In particular, catalyst residues can be removed from a polymer solution subjected to a hydrogenation reaction by the method of the present invention, if necessary, and the hydrogenated polymer can be easily isolated from the solution. for example,
A method in which a polar solvent such as acetone or alcohol, which is a poor solvent for the hydrogenated polymer, is added to the reaction solution after hydrogenation to precipitate and recover the polymer. This can be carried out by distillation and recovery, or by directly heating the reaction solution and distilling off the solvent.

The hydrogenation method of the present invention is characterized in that the amount of hydrogenation catalyst used is smaller. Therefore, even if the hydrogenation catalyst remains in the small polymer, it does not significantly affect the physical properties of the hydrogenated polymer obtained, and most of the catalyst is decomposed and removed during the isolation process of the hydrogenated polymer. Since it is removed from the coalescence, no special operations are required to deash or remove the catalyst, and it can be carried out in an extremely simple process.

〔Effect of the invention〕

As described above, the method of the present invention makes it possible to efficiently hydrogenate olefinically unsaturated double bonds, and in particular, it is possible to hydrogenate polymers having olefinically unsaturated double bonds under mild conditions using a highly active catalyst. Furthermore, it has become possible to hydrogenate the unsaturated double bonds of the conjugated diene units of a copolymer of a conjugated diene and a vinyl-substituted aromatic hydrocarbon very selectively. Furthermore, the long-term storage stability of the catalyst is increased, it is less susceptible to the effects of catalyst preparation conditions and impurities in the system, it eliminates the need to prepare the catalyst immediately before hydrogenation, and it also streamlines the process.

Furthermore, the hydrogenated polymer obtained by the method of the present invention can be used as an elastomer, thermoplastic elastomer, or thermoplastic resin with excellent weather resistance and oxidation resistance, and can also be added with ultraviolet absorbers, oils, fillers, etc. It is used by adding agents or blending with other elastic bodies or resins, and is extremely useful in the T industry.

〔Example〕

The present invention will be specifically explained below with reference to Examples, but the present invention is not limited thereto.

Reference Example 1 200 ml of anhydrous ether was added to a 1 g three-necked flask equipped with a stirrer, dropping funnel and reflux condenser. Replace the device with dry helium and add 17.4 g of small pieces of lithium wire.
(2.5 mol) was cut into a flask and the ether 3
After a small amount of a solution of 00+nl and 157 g (1 mol) of bromobenzene was added dropwise at room temperature, the entire amount of the ether solution of bromobenzene was gradually added under reflux.

After the reaction was completed, the reaction solution was filtered under a helium atmosphere to obtain a colorless and transparent phenyllithium solution.

2β with stirrer and addition funnel replaced with dry helium
99.6 g (0.4 mol) of dichlorobis(cyclopentadienyl)titanium and 500+ nl of anhydrous ether were added to a Mitsuro flask. The previously synthesized ether solution of phenyllithium was added dropwise over about 2 hours while stirring at room temperature. The reaction mixture was filtered in air, and the insoluble portion was washed with dichloromethane. The filtrate and washing liquid were combined and the solvent was removed under reduced pressure.

After dissolving the residue in a small amount of dichloromethane, petroleum ether was added to perform recrystallization. The obtained crystals were separated by filtration, the filtrate was concentrated again, and the above operation was repeated to obtain diphenylbis(η-cyclopentadienyl)titanium. The yield was 120 g (90% yield). The obtained crystals are orange-yellow needle-shaped, have good solubility in toluene and cyclohexane, have a melting point of 147°C, and have an elemental analysis value of:
C,79,5,H.

6, L; Ti, 14.4.

Reference Example 2 Synthesized in the same manner as Reference Example 1 except that p-bromotoluene was used instead of bromobenzene, and di-lytolylbis(η-
cyclopentadienyl) titanium was obtained (yield 87%)
). This substance is in the form of yellow crystals, has good solubility in toluene and cyclohexane, and has a melting point of 145°C.
Elemental analysis value: C180,0; H,6,7; Ti,
It was 13.3.

Reference Example 3 Synthesis was carried out in the same manner as in Reference Example 1 except that 4-bromo-0-xylene was used instead of bromobenzene to obtain di-3,4-xylylbis(η-cyclopentadienyl)titanium (yield: 83%). This substance is in the form of yellow crystals, has good solubility in toluene and cyclohexane, has a melting point of 155°C, and has an elemental analysis value of C, 80,6; H, 7,2.
; Tf was 12.2.

Reference Example 4 Synthesis was carried out in the same manner as in Reference Example 1 except that p-bromoethylbenzene was used instead of bromobenzene, and bis(4-ethylphenyl)bis(η-cyclopentajenyl)titanium was obtained (yield 8o %). This thing is a yellow crystal,
Solubility in toluene and cyclohexane is good, melting point 154°C1 elemental analysis value; C, 80, 4; H
, 7,3; Ti, 12.3.

Reference example 5 500g of cyclohexane in a 2Ω autoclave,
100 g of 1,3-butadiene monomer and 0.05 g of n-butyllithium were added and polymerized at 60° C. for 3 hours with stirring to synthesize a butadiene homopolymer. The obtained butadiene polymer contained 13% of 1,2-vinyl bonds and was analyzed by GPC
The weight average molecular weight measured was approximately 150,000.

Reference Example 6 Polymerization was carried out in the same manner as Reference Example 1 except that isoprene was used instead of 1,3-butadiene, and the 1,2-vinyl bond was 10%.
An isoprene polymer having a weight average molecular weight of about 150,000 was obtained.

Reference Example 7 400 g of cyclohexane, 70 g of 1,3-butadiene monomer, 30 g of styrene monomer, 0.03 g of n-butyllithium, and 0.9 g of tetrahydrofuran were simultaneously added to an autoclave and polymerized at 40°C for 2 hours.

The obtained polymer was a completely random copolymer of butadiene/styrene having a 1,2-hinyl bond a ratio of 50% in brush units and an average molecular weight of 200,000.

Reference Example 8 4000 g of cyclohexane, 1509 styrene monomer and 1.109 g of n-butyllithium were added to an autoclave and polymerized at 60'C for 3 hours, then 700 g of 1,3-butadiene monomer was added and the mixture was heated at 60°C for 3 hours. Polymerized for hours. Finally, add 150g of styrene monomer and
Polymerization was carried out at °C for 3 hours. This living polymer solution was poured into a large amount of methanol to deactivate and precipitate, and then vacuum-dried at 60'C for 50 hours.

The obtained polymer had a bound styrene content of 30%, a blocked styrene content of 28%, a butadiene unit 1,2-vinyl bound gold content of 12% (polymer conversion q8%), and a number average molecular weight of approximately 60,000. It was a styrene-butadiene-styrene type block copolymer.

Reference Example 9 Using exactly the same method as in Reference Example 8 except that 35 times the mole of tetrahydrofuran relative to n-butyllithium was added, the bonded styrene content was 3a%, the block styrene content was 24%, and 1,2-vinyl butadiene units were prepared. Contains bonds! 3
A styrene-butadiene-styrene type block copolymer having a molecular weight of 9% (23% in terms of total polymer) and a number average molecular weight of about 60,000 was synthesized.

Reference example 10 8000 g of cyclohexane in an autoclave.

1.200 g of 3-butadiene monomer, n-butyllithium L, 10 g and tetrahydrofuran in a molar ratio of n
-BuLi/THF=added at a ratio of 1/40, 7
Polymerize at 0°C for 45 minutes, then add 300 ml of styrene monomer.
g for 60 minutes, then 1,3-butadiene monomer 12
00 g was added and polymerized for 150 minutes, and finally 300 g of styrene monomer was added and polymerized for 60 minutes to synthesize a butadiene-styrene-butadiene-styrene type block copolymer. This living polymer solution was poured into a large amount of methanol to deactivate and precipitate, and then vacuum-dried at 60° C. for 50 hours. This product contains 30% bound styrene content, 28% blocked styrene content, and 1,2-vinyl bond of butadiene unit! It was a block copolymer with a number average molecular weight of 35% (25% in terms of total polymer) and a number average molecular weight of about 12.

Reference Example 11 A butadiene-styrene-butadiene-styrene type living block copolymer was polymerized in exactly the same manner as in Reference Example 10. This product had 83 mmol of living lithium per 100 g of polymer, and when a portion was isolated and analyzed, the content of bound styrene was 30%, the content of blocked styrene was 27%, and the 1,2-vinyl bond of the butadiene unit The gold content was 34% (24% in terms of total polymer) and the number average molecular weight was about 120,000.

The polymer used as the catalyst component (C) is the following polymer or a polymer obtained by the preparation method.

(1) Polymer A Nippon Soda reconstituted 1,2-polybutadiene (Nisso
B-1000) 1.2-vinyl bond gold content = 85% (
2) Polymer B Nippon Petrochemical ■Reconcentrate 1,2-polybutadiene (B-7
00) 1.2-vinyl bond metal content = 57% (3) Polymer C 1.2-syndiotactic polybutadiene (RB-700) manufactured by Nippon Synthetic Rubber ■ 1.2-vinyl bond metal content -
95% (4> Polymer D (synthetic liquid 1.2-PB) 250
123.2 g of cyclohexane in m1 autoclave
After adding 16.8 g of butadiene, n-BuLiO, 20
g and 1,2-dipiperidinoethane (DPE)6
．． Add 12g (DPE/Li molar ratio = 10.0) and
Polymerization was carried out at 8°C for 3 hours.

The resulting polymer had a 1,2-vinyl bond content of 100 g.
, number average molecular ff16100.

(5) Polymer E In the polymerization of Polymer D, isoprene was used instead of butadiene, and n-BuLiffl and DPE were each added at 0.0%.
Polymerization was carried out in the same manner except that the amounts were changed to 25 g and 7.65 g.

The obtained polymer had 5% 1,4 bonds, 22% 1,2-vinyl bonds, 73% 3,4 bonds, and a number average molecular weight of ff158.
It was 00.

(6) Polymer F Idemitsu Petrochemical ■ Antacid polybutadiene (R-45M) 1
, 2-vinyl bond alloy content - 2 3%) Polymer G The styrene-butadiene-styrene tri-block copolymer polymerized in Reference Example 8 with a 1,2-vinyl bond alloy content of 12% (polybutadiene portion ), with a number average molecular weight of approximately 60,000.

(8) Polymer H A styrene-butadiene-styrene tri-block copolymer polymerized in Reference Example 10, with a 1,2-vinyl bond content of 35% (polybutadiene moiety) and a number average molecular weight of approximately 12
Ten thousand things.

Examples 1 to 5 1-hexene and cyclohexene were diluted with cyclohexane, adjusted to a concentration of 15%, and subjected to hydrogenation reaction.

In a sufficiently dry autoclave with a capacity of 21 and equipped with a stirrer,
After 1000 g of the above olefin compound solution was charged and degassed under reduced pressure, the mixture was replaced with hydrogen and maintained at 30° C. with stirring.

Next, dichlorobis(cyclopentadienyl)titanium (Kanto Chemical System) was used as the catalyst component (A), and Reference Examples 1 to
100 ml of a cyclohexane solution containing 0.1 mmol each of the titanocene compounds synthesized in step 4 and the catalyst component (B
) as catalyst component (C) and a cyclohexane solution containing 0.4 mmol of n-butyllithium as catalyst component (C).
The entire amount of the catalyst solution (Li/Ti molar ratio = 4) mixed for 15 minutes at 25°C under a hydrogen pressure of 2.0 kg/cTl in the presence of 3.6 g was charged into an autoclave, and 5.0 kg/cTl was mixed in the presence of 3.6 g.
Dry gaseous hydrogen of cd was supplied and the hydrogenation reaction was carried out for 1 hour with stirring. After the reaction solution was returned to normal temperature and pressure, the hydrogenation rate was determined by gas chromatography. The results are shown in Table 1.

Comparative Example 1 The same procedure as in Example 1 was carried out except that the catalyst (C) component was not added. The results are shown in Table 1.

Comparative Example 2 The same procedure as in Example 1 was conducted except that Polymer F was used as the catalyst (C) component. The results are shown in Table 1.

Examples 6 to 12 The various polymers obtained in Reference Examples 5 to 10 were diluted with purified and dried cyclohexane, the polymer concentration was adjusted to 5% by weight, and the mixture was subjected to a hydrogenation reaction. In addition, the Ping polymer solution obtained in Reference Example 11 was diluted with purified and dried cyclohexane,
The living polymer concentration was adjusted to 5% by weight and subjected to hydrogenation reaction.

In a sufficiently dry autoclave with a capacity of 2 g and equipped with a stirrer,
100 of the above various polymer solutions or lipping polymer solutions
0.092 g of 2,6-di-t-butyl-p-cresol was added to deactivate the active lithium, and after degassing under reduced pressure, the mixture was replaced with hydrogen and maintained at 60° C. with stirring.

Next, 50 ml of a cyclohexane solution containing 0.0125 mmol of bis(cyclopentadienyl)titanium dichloride as the catalyst component (A) and cyclohexane containing 0.1 mmol of 4-methylphenyllithium synthesized in Reference Example 2 as the catalyst component (B) were added. The solution was used as catalyst component (C) in the presence of 18 g of polymer C, 25°C, 2.0 kg/
Catalyst solution (1-1) mixed for about 30 minutes under hydrogen pressure of cd
7zri7rratio-18) was charged into an ormil crepe, and 3 y"cti of dry hydrogen gas was supplied to the 5.0", and the hydrogenation reaction was carried out with stirring "F' for 1 hour. Return the reaction solution to normal temperature and pressure and remove it from the autoclave.
A large amount of methanol was added to precipitate the polymer, which was filtered and dried to obtain a white hydrogenated polymer. The hydrogenation rate of the obtained hydrogenated polymer was determined from infrared absorption spectra 1 to 1.
-4841@IFj,) shown in Table 2.

Comparative Example 3 The same procedure as in Example 9 was carried out except that the catalyst was prepared without adding the catalyst (C) component. The results are shown in Table 2.

Comparative Example 4 The same procedure as in Example 1 was carried out except that a polymer was used as the catalyst (C) component. The results are shown in Table 2.

(Left below) Example 13 The Ping polymer solution obtained in Reference Example 11 was diluted with purified and dried cyclohexane to give a living bomber concentration of 5.
Pour 1000 g of the mold weight percent, then add 30 ml of a cyclohexane solution containing benzyl alcohol of 0.415 mmoρ to deactivate the living polymer, degas under reduced pressure, replace the liquid with hydrogen, and heat to 60°C with stirring. held.

Next, 50 ml of a cyclohexane solution containing 0.01 mmol of diphenylbis(η-cyclopentadienyl)titanium as the catalyst component (A) and a cyclohexane solution containing 0.05 mmol of n-butyllithium as the catalyst component (B) were catalyzed. Poly as component (C)? -A0.5
The catalyst solution (Li/Ti = 5) mixed for about 30 minutes at 25°C and under a hydrogen pressure of 2.0 kg/cJ in the presence of 2.0 kg/cJ was charged into an autoclave, and the rest was carried out in the same manner as in Examples 6 to 12. I did it. The results obtained are shown in Table 3.

Example 14 The same procedure as Example 13 was carried out except that Polymer B was used instead of Polymer A.

Example 15 The same procedure as Example 13 was carried out except that Polymer D was used instead of Polymer A.

Example 16 The same procedure as Example 13 was carried out except that Polymer E was used instead of Polymer A.

Example 17 The same procedure as Example I3 was carried out except that Polymer H was used instead of Polymer A.

Comparative Example 5 The same procedure as Example 13 was carried out except that Polymer F was used instead of Polymer A.

Comparative Example 6 The same procedure as Example 13 was carried out except that Polymer G was used instead of Polymer A.

(Left below) Example 18 Catalysts (A), (B),
Component (C) was mixed and the mixed solution was immediately stored in a refrigerator at 10° C. to prepare 5 batches of each.

The storage time is 1 hour, 3 days, 10 days, and 1 month, respectively.

Hydrogenation was carried out in the same manner as in Example 11 for 3 months. The results are shown in Table 4.

Comparative Example 7 Example 18 except that the catalyst (C) component was not added.
Hydrogenation was carried out in the same manner. The results are shown in Table 4.

Comparative Example 8 Catalysts (A), (B),
Component (C) was mixed and hydrogenated in the same manner as in Example 18. The results are shown in Table 4.

(The following is a blank space) Example I9 Various polymers obtained in Reference Example 8 were diluted with purified and dried cyclohexane, the polymer concentration was adjusted to 5% by weight, and the mixture was subjected to a hydrogenation reaction.

1000 g of the above polymer solution was charged into a sufficiently dried 2 g autoclave equipped with a stirrer.

Then 2.6-di-t-butyl-p-cresol was added to 2.
200 ml of a cyclohexane solution containing 5 mmol was mixed with a cyclohexane solution containing 2.75 mmol of n-butyllithium to obtain 2,6-di-t-butyl-4-methylphenoquinlithium (catalyst component (B)). In this system, 0.313 mmol of bis(cyclopentadienyl)titanium dichloride was added as the catalyst component (A), and
As C), 5 batches each containing 20 g of polymer C were prepared. The storage time was 1 hour, 3 days, and 10 days, respectively.
Hydrogenation was carried out in exactly the same manner as in Example 9 for 1 day, 1 month, and 3 months. The results are shown in Table 5.

Comparative Example 9 Hydrogenation was carried out in exactly the same manner as in Example 19, except that the catalyst component (C) was not added. The results are shown in Table 5.

(Leaving space below) Test values Examples 1.6, 10.17 and Comparative Examples 1 and 4.6 were repeated by changing the experimental port, the solvent used, and the monomer purification port. The variation in hydrogenation rate was investigated.

(Margin below)

Claims (1)

[Claims] 1. A method of hydrogenating the olefinically unsaturated double bonds in the compound by contacting the compound containing an olefinically unsaturated double bond with hydrogen in an inert organic solvent, comprising: (A ) At least one metallocene compound represented by the following general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (However, R^1 and R^2 are C_1 to C_1_2 hydrocarbon groups, aryloxy groups, alkoxy groups, halogen groups) and a carbonyl group, R^1, R
^2 may be the same or different. Further, M represents a metal selected from Ti, Zr, and Hf. ) (B) When reducing with at least one compound containing lithium, sodium, potassium, aluminum, zinc, or magnesium that has reducing ability, (C) The overall olefinicity of the amount of olefinically unsaturated double bonds in the side chain. The fraction relative to the amount of unsaturated double bonds is 0.3 to 1
A method for hydrogenating an olefinically unsaturated double bond-containing compound, characterized in that the hydrogenation catalyst comprises an olefinically unsaturated double bond-containing polymer coexisting therein. 2. The hydrogenation method according to claim 1, wherein the olefinically unsaturated double bond-containing compound is a conjugated diene polymer or a copolymer of a conjugated diene and a vinyl aromatic hydrocarbon. 3. The hydrogenation method according to claim 2, wherein the conjugated diene is 1,3-butadiene and/or isoprene, and the vinyl aromatic hydrocarbon is styrene and/or α-methylstyrene. 4. The catalyst is (A) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ and/or (C_5H_5)_2TiCl_2 and (B) n-butyllithium and/or sec-butyllithium and/or triethylaluminum and/or ethylmagnesium chloride and (C
2. The hydrogenation method according to claim 1, wherein the catalyst is a liquid polybutadiene having a 1,2-vinyl bond content of 40% or more.