JPH0496904A - Hydrogenation method for olefin compounds - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

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. .

[Prior Art] 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 and generally has lower activity than homogeneous catalysts, requires a large amount of catalyst to carry out the desired hydrogenation reaction, and is carried out at high temperature and pressure. Therefore, it becomes uneconomical. On the other hand, with the latter type of homogeneous catalyst, the hydrogenation reaction usually proceeds in a homogeneous system, so compared to a heterogeneous system, it has higher activity and requires less catalyst usage, and has the characteristics of being able to perform hydrogenation at lower temperatures and pressures. On the other hand, the stability of the catalyst itself is not sufficient due to the complicated catalyst preparation, the reproducibility is poor, and undesirable side reactions are likely to occur.
are doing. Therefore, there is currently a strong desire to develop a hydrogenation catalyst that is highly active and easy to handle.

On the other hand, polymers containing olefinically unsaturated double bonds are advantageously used for vulcanization, etc., but on the other hand, such double bonds have poor stability such as weather resistance and oxidation resistance. It has its drawbacks. These disadvantages of poor stability can be improved significantly by hydrogenating the polymer to eliminate unsaturated double bonds in the polymer chain.However, when hydrogenating the polymer, low molecular weight compounds Compared to hydrogenation of hydrogen, it is difficult to hydrogenate due to the effects of the viscosity of the reaction system and steric hindrance of the polymer chain.It is extremely difficult to physically remove the catalyst after the hydrogenation is completed. difficult and virtually impossible to separate completely;
There are some drawbacks such as. Therefore, in order to economically hydrogenate polymers, it is strongly desired to develop a highly active hydrogenation catalyst that exhibits activity at a level that does not require deashing, or a catalyst that can be deashed extremely easily. There is.

The present inventors have already developed a method for hydrogenating an olefin compound by combining a specific titanocene compound and an alkyl lithium (JP-A-61-33132, JP-A-1-53851).
No.), a method of hydrogenating an olefinically unsaturated (co)polymer by combining a metallopine compound with H-organic aluminum, zinc, and magnesium (JP-A No. 61-28507, 62-
209102. q, No. 62-209103), a method of hydrogenating an olefinically unsaturated group-containing Hing polymer using a combination of a specific titanocene compound and an alkyl lithium (JP-A-81-117706, JP-B No. 63-5)
No. 402) etc. have already been invented.

However, these methods have the disadvantage that when the hydrogenation temperature becomes relatively high, the catalyst is deactivated and the activity decreases. Therefore, especially when hydrogenating polymers, it is not possible to increase the reaction temperature to reach quantitative hydrogenation, and it is necessary to keep the polymer solution concentration low to remove heat or to control hydrogen consumption. Since it was necessary to suppress stirring, there was a desire to develop a catalyst or method that was more stable at high temperatures.

(Problems to be solved by the present invention) The present invention is a heat-resistant highly active water that is stable and easy to handle, exhibits activity with a very small amount of use during hydrogenation reactions, and is resistant to deactivation even at relatively high temperatures. The problem to be solved is to discover a method to obtain hydrogenated polymers with excellent weather resistance, oxidation resistance, and ozone resistance.

(Means and effects for solving the problem) The present invention provides (A
) A hydrogenation catalyst consisting of a specific metallocene compound and (B) at least one of lithium, sodium, potassium, aluminum, zinc or magnesium-containing compounds having a reducing ability, which is not easily deactivated even at relatively high temperatures; It exhibits high activity even in extremely small amounts, and selectively hydrogenates unsaturated double bonds in polymers containing olefinically unsaturated double bonds under mild conditions and in amounts that do not require deashing. This is based on the surprising fact that it is possible.

In other words, the present invention is a method of preparing an olefinically unsaturated double bond-containing compound in an inert organic solvent, and (8) containing at least five types of metallochemical reactions represented by , R is a methyl group, R1, R- is C to C12
R represents a group selected from a hydrocarbon group, an auroxy group, an alkoxy group, a halogen group, and a carbonyl group;
, R2 may be the same or different.

Further, M represents a metal selected from Ti, Zr, and 1f. ) (B) In the presence of a catalyst comprising at least one of lithium, sodium, potassium, aluminum, zinc or magnesium-containing compounds having a reducing ability, the olefinically unsaturated double bonds in the compound are brought into contact with hydrogen. The present invention relates to a method for hydrogenating olefins, which is characterized by hydrogenation.

Meta I-I in which R is hydrogen in general formula (A) according to the present invention
The present inventors have proposed a method for hydrogenating the A-lenoic unsaturated 2-l bond in the small bond gold i-1,000 combination by combining the II' compound and (8). (JP-A-61-33132, JP-A-61-28507, JP-A-62-209102, JP-A-62-209103, etc.).

The present inventors have maintained the activity of this prior olefin hydrogenation catalyst system, prevented catalyst deactivation due to temperature rise, and improved the production rate as the polymer solution concentration increased due to the decrease in solution viscosity due to temperature increase. As a result of further intensive studies on the hydrogenation method that leads to
Comparing the catalyst using a combination of It was discovered that the deactivation of the catalyst could be prevented by as much as 1 J, and the production volume could be significantly improved by increasing the temperature.
This has led to the completion of the present invention.

The A renoine compound hydrogenation catalyst component (8) according to the present invention is - general ().

(However, R is a methyl group, R1, R2 are C-C12
represents a group selected from a hydrocarbon group, an auroxy group, an alkoxy group, a halogen group and a carboxyl group,
R2 and R3 may be the same or different. Also, M is Ti
, Zr, and Hf. ) The C1-C12 hydrocarbon group of R1R2 includes, for example, a rule hydrocarbon group, in which one or more of R3 and R5 is hydrogen, and n=Q or 1). If all of R to R5 are alkyl groups, it is difficult to synthesize with good yield due to steric hindrance, so it is not preferred.

Furthermore, it is difficult to synthesize a compound in which the alkyl hydrocarbon group is located in the or-l position with respect to the central metal.

Specific examples of such catalysts (A) include bis(pentamethylcyclopentadienyl)titanium dimethyl, bis(
pentamethylcyclopentagenyl) titanium diethyl, bis(pentamethylcyclopentagenyl) titanium di-n-butyl, bis(pentamethylcyclopentagenyl) titanium di-5ec-butyl, bis(pentamethylcyclopentagenyl) titanium diethyl,
Bis(pentamethylcyclopentagenyl) titanium dioctyl, bis(pentamethylcyclopentagenyl) titanium dimethoxide, bis(pentamethylcyclopentagenyl) titanium dioctyl, bis(pentamethylcyclopentagenyl) titanium dimethoxide 1 toxide, his(pentamethylcyclopentagenyl) titanium diphenyl, his(pentamethylcyclopentagenyl) titanium di-m-tolyl, bis(pentamethylcyclopentagenyl) titanium di-p-tolyl, his-penta methylcyclopentagenyl) titanium di..., β-xylyl, bis(pentamethylcyclopentagenyl) titanium di-4-ethylphenyl, his(
pentamethylcyclopentadienyl) titanium di-4
-butylphenyl, bis(pentamethylcyclopentadienyl) titanium di-4-hexylphenyl, bis(
pentamethylcyclopentagenyl) titanium diphenoxide, hiss (pentamethylcyclopentagenyl)
Titanium dichloride, Bis(pentamethylcyclopentagenyl) titanium dichloride, Bis(pentamethylcyclopentagenyl) titanium dichloride, Dos(pentamethylcyclopentagenyl) titanium dichloride, His(pentamethylcyclopentagenyl) 1
his(pentamethylcyclopentagenyl) titanium chloride ethoxide, his(pentamethylcyclopentagenyl) titanium chloride ethoxide, his(pentamethylcyclopentagenyl) titanium chloride 1 tuxite, his (pentamethylcyclopentagenyl) titanium dibenzylhis (pentamethylcyclopentagenyl) zirconium dimethyl, bis(pentamethylcyclopentagenyl) zirconium diethyl, bis(pentamethylcyclopentagenyl) zirconium-n-butyl, Bis(pentamethylcyclopentadienyl)zirconium disec ~butyl, his(pentamethylcyclopentadienyl)zirconium dihexyl, bis(pentamethylcyclopentadienyl)zirconium dioctyl, bis(pentamethylcyclopentadienyl)zirconium laminate Methoxide, bis(pentamethylcyclopentagenyl) zirconium jetoxide, his(pentamethylcyclopentagenyl) zirconium 11 hexide, bis(pentamethylcyclopentagenyl) zirconium diphenyl, his(pentamethylcyclopentagenyl) Zirconium 2-rubispentamethylcyclopentadienyl)zirconium di-p-tolyl, His(pentamethylcyclopentadienyl)zirconium-m,p-xylyl, Bis(pentamethylcyclopentagenyl)zirconium di-4-
Ethylphenyl, bis(pentamethylcyclopentajenyl) zirconium diphenoxide, bis(pentamethylcyclopentagenyl) zirconium dichloride,
His(pentamethylcyclopentagenyl) zirconium dichloride, bis(pentamethylcyclopentagenyl) zirconium dichloride, bis(pentamethylcyclopentagenyl) zirconium dioctyl, bis(pentamethylcyclopentagenyl) zirconium dicarbonyl, bis (pentamethylcyclopentadienyl) zirconium chloride methyl, his(pentamethylschiff 1" pentadienyl) hanonium dimethyl, bis(
Pentamethylschiff (coventadienyl) hafnium sulfur
Chyl, bis(pentamethylcyclopentagenyl) hafnium di-n-butyl, bis(pentamethylcyclopentagenyl) hafnilamushi 5eC-butyl, his(pentamethylcyclopentagenyl) dihexyl, bis(pentamethylcyclopentagenyl) Hafnilamushi methoxide, bis(pentamethylcyclopentadienyl) hafnium jetoxide, bis(pentamethylcyclopentadienyl) hafnium jetoxide, bis(pentamethylcyclopentadienyl) hafnium diphenyl, bis(pentamethylcyclopentagenyl) genyl) hafnium di-
m-tolyl, his(pentamethylcyclopentadienyl) hafnium sil-tolyl, bis(pentamethylcyclopentadienyl) hafnium di m,p-xylyl, bis(pentamethylcyclopentagenyl) hafnium diphenoxide, bis-tolyl pentamethylcyclopentagenyl) hafnium difluorite, bis(pentamethylcyclopentagenyl) hafnium dichlorite, bis(
Bentameburucyclobentacyl) hafnium dichlorite, bis(pentamethylcyclopentadienyl) hafnium dichlorite, bis(pentamethylcyclopentadienyl) hafnium difluoronyl, bis(pentamethylcyclopentadienyl) hafnium Examples include methyl chloride. These can be used alone or in combination with each other. Among these metallocene compounds, those that have high hydrogenation activity toward olefinically unsaturated double bonds in olefin compounds and can selectively hydrogenate unsaturated double bonds under mild conditions include bis( Pentamethylcyclopentagenyl〉Titanium dimethyl, His(pentamethylcyclopentagenyl) titanium di-n-butyl, Bis(pentamethylcyclopentagenyl) titanium dichlorite, His(pentamethylcyclopentagenyl) titanium. cumdiphenyl, bis(pentamethylcyclopentadienyl) titanium di-rootnol, disu(pentamethylcyclopentadienyl) ftanium cycarbonyl, his(pentamethylcyclopentadienyl) hafnium cyclophyte, his(pentamethylcyclopentadienyl) Methylcyclobenkyl) hafium dibromite, bis(pentamethylcyclopentadienyl) hafnium diphenyl, his(pentamethylcyclopentadienyl) hafnium di-p-tolyl, his(pentamethylcyclopentadienyl) ) hafnium di-p-tolyl, bis(pentamethylcyclopentadienyl)zirconium dimethyl, bis(pentamethylcyclopentadienyl)zirconium di-n-butyl, bis(
pentamethylcyclopentagenyl) zirconium dichlorite, bis(pentamethylcyclopentagenyl)
Examples include zirconium dichlorite, bis(pentamethylcyclopentadienyl)silcoum diphenyl, his(pentamethylcyclopentagenyl)zirconium di-p-tolyl, and bis(pentamethylcyclopentagenyl)zirconium dicarbonyl. The more preferred compounds are those that can be handled fairly stably and exhibit the highest activity when combined with the reducing metal compound (B), such as di(bentameburucyclopentacyl)titanium cyclolide, bis(pentamethyl cyclopentadienyl) titanium di-p-tolyl, and the latter is the most preferred because it has excellent solubility.

On the other hand, as the catalyst component (8), an organic metal compound capable of reducing the metallocene compound of the catalyst component (A), such as an organic lithium compound, an organic aluminum compound, an organic zinc compound, an organic magnesium compound, an organic sodium compound, an organic The polymer can be hydrogenated by using potassium compounds and the like alone or in combination with each other.

Examples of organolithium compounds include the general formula R7-Li (
However, R7 is a C to G hydrocarbon group, an aryloxy group, or an alkoxy group, and the C1 to C12 hydrocarbon group is alkyl hydrocarbon, and one or more of R3 to R5 -[- is hydrogen. and n=Q or 1. ) Compounds shown in
C-butyllithium, isobutyllithium, n-benthyllithium, n-hexyllithium, phenyllithium, m-tolyllithium, p-tolyllithium, xylyllithium, methoxylithium, ethoxylithium, n-
Propoxylithium, isopropoxylithium, n-butoxylithium, 5ec-butoxylithium, t-11
~xylithium, pentyloxylithium, hexyloxylithium, octyloxylithium, phenoxylithium, 4-methylphenoxylithium, benzyloxylithium, 4-methylbenzyloxylithium, and the like.

It is also used as a compound obtained by reacting a phenolic stabilizer with an alkyl lithium. Specific examples of such phenolic stabilizers include 1
-oxy-3-methyl-4isopropylene, 2,
6-tert-butylphenol, 2,6-tert
ert-butyl-4-ethylphenol, 2,6-tert-ablu p-cresol, 2,6-te
rt-butyl-4-n-butylphenol, 4-hydroxymethyl-2,6-di-tert-butylphenol,
Butylhydroxyanisole, 2-(1-methylcyclohexyl)4,6-dimethylphenol, 2,4-dimethyl-6tert-butylphenol, 2-methyl-4
, 6-ditunylphenol, 2,6-tert-butyl-α dimethylamino-p-cresol, methylene-
Bis(dimethyl-4,6-phenol), 2,21-
Methylene-bis-(4-methyl-6-tert-butylphenol), 2,2'-methylene-bis-(4-methyl-6-cyclohexylphenol), 2,2'
-methylene-bis-(4-ethyl-6tert-butylphenol), 4,4'-methylenehis-(2,
6 sheets tert-butylphenol), 2.2'-
Examples include methylene-his-(6-α methylhensyl-p-cresol).

The most widely used 2,6-tert-butyl-p-cresol has a hydroxyl group of -OLi.
Butyl-4-methylnoeno-[dilithium] is particularly preferably used.

Also 1-limethylsilyllithium, diethylmethylsilyllithium/dimethylethylsilyllithium, triethylsilyllithium, triphenyllithium, trimethylsiloxylithium, diethylmethylsilyllithium,
Organosilicon lithium compounds such as triethylsiloxylithium and triphenylsiloxylithium may also be used.

As an aluminum compound, trimethylaluminum,
Triethylaluminum, 1-isobutylaluminum, triphenylaluminum, diethylaluminum chloride, ethylaluminum dichlorite, methylaluminum sesquichloride, ethylaluminum sesquichloride, diethylaluminum hydride, triphenyl Examples include aluminum, tri(2-ethylhexyl)aluminum, methylaluminoxane, ethylfluminoquiline, etc.; examples of zinc compounds include diethylzinc, bis(cyclopentagenyl)zinc, diphenylzinc, etc.; and magnesium compounds: Dimethylmagnesium, diethylmagnesium, methylmagnesium bromide, ethylmagnesium chloride, ethylmagnesium bromide, ethylmagnesium chloride, phenylmagnesium bromide, phenylmagnesium chloride, dibutylmagnesium, t-butylmagnesium chloride, etc. Examples of the sodium compound include methyl Sodium, ethyl sodium, n-propyl sodium, isopropyl sodium, n-butisib 1
~lium, 5ec-butyl sodium, isobutyl sodium, n-benzyl sodium, n-hexyl sodium, benzyl sodium, phenyl sodium, thorium, na1~su1cumno-notalene, l\xynyl J cry~lium , -71 nylsilyl sodium, cyclopentadienyl sodium, pentamebylcyclopentacyl nyl-I-lium, trimethylsilyl sodium, trimethylsilyl sodium, etc., and potassium compounds include methylpotassium,
Examples include ethyl sodium, triphelmethyl potassium, phenylethyl potassium, and the like. In addition to these 1-
Lithium aluminum hydride, lithium aluminum hydride, diisobutyl sodium aluminum hydride, tri(t-butoxy) lithium aluminum hydride, triethyl sodium aluminum hydride, diisobutyl sodium aluminum bitite, isobutyl sodium aluminum hydride, triethyl sodium aluminum hydride, triethoxy sodium aluminum hydride , triethyllithium aluminum hydride, etc.
A reducing agent containing more than one metal may also be used.

These are:1. It is not difficult to use a mixture of lead materials with phase q, or two or more types of lead materials with phase q may be used.

In order to exhibit the highest hydrogenation activity and selectively hydrogenate olefinically unsaturated double bonds, r) acyllithium is most preferred.

As the catalyst, it is preferable to use a mixture of catalyst component (A) and catalyst component (8) in advance because it has high activity. The hydrogenation reaction can also be carried out by separately adding either the catalyst component (8) or the catalyst component (B) to the hydrogenated substance solution first.

In addition, when mixing the catalyst component (A) and the catalyst component (B), the ratio of the amount of olefinically unsaturated double bonds in the side chain to the total amount of olefinically unsaturated double bonds as the catalyst component (C) A polymer having a molecular weight of 0.3 to 1 may be added. An example of a monomer used in the preparation of these catalyst components (C) is a conjugated diene, generally having from 4 to about 12 carbon atoms. Specific examples include 1,3-butadiene, isoprene, 2,3-dimethylbutadiene, 1,3-pentacine, 2-methyl 1,3-pentadiene, 1,3-hexylene, 4, 5
Side del-1,3-octadiene, 3-1 til L3-'
) j katsien, etc. These may be used alone or in combination of two or more. It can be advantageously developed industrially,
Particularly preferred are 1,3-butadiene and isoprene, which are easy to use manually, and polybutadiene, polyisoprene, and butadiene/isoprene copolymers are preferred. Alternatively, norfornodiene, dicyclopentadiene, 2,3-dihydrodicyclopentadiene, and alkyl substituted products thereof may be used alone or in copolymerization.

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 set to 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 often liquid at room temperature and has a number average molecular weight of 50.
A value of 0 to 10,000 is preferable.

When the number average molecular weight is 10,000 or more, there is no particular problem in terms of performance, except that handling as a liquid becomes difficult. 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 in the range of 0.3 to 1, but as long as it is within this range, it may have a functional group such as a hydroxyl group, carboxyl group, or amine group at the end.

To give a specific example, polybutadiene has 30 to 100 1.2-vinyl bonds compared to all olefinically unsaturated double bonds (cis 1,4 bonds, trans 1.4 bonds, 1,2-vinyl bonds). % is required. In addition, in the case of polyisoprene, for all olefinically unsaturated double bonds (cis 1,4 bonds, trans 14 bonds, 1,2 bonds, 3,4 bonds), the olefinically unsaturated double bonds in the side chains ( 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, and the stability is poor, and if not handled properly, problems may arise in reproducibility.

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-amineethylstyrene, and styrene is particularly preferred. Specific examples of copolymers include butadiene/styrene copolymers,
Isoprene/styrene copolymers and the like are most preferred.

These copolymers may be random, block, star-shaped blocks, tapered blocks, etc., and are not particularly limited. Also, the amount of bonded aromatic vinyl compound is 70%
The following are preferred. If it exceeds 10%, the amount of conjugated diene moieties will be substantially reduced, and the effect of making the reduction catalyst safer will be small. Of course, it is necessary that the ratio of the olefinically unsaturated double bonds φ in the side chain of the conjugated 912 parts to the total olefinic double bonds is 0.3 to 1.

These catalyst components (C) can be used for radical polymerization, cationic polymerization,
Polymerization may be carried out using any known method such as anionic polymerization or coordinated anionic polymerization, but in order to increase the amount of olefinically unsaturated double bonds in the side chain, organic lithium or It is preferably obtained by living anion polymerization using an organic sodium compound as a catalyst, by coordination anion polymerization using a cobalt-based Ziegler type catalyst, or by copolymerizing ethylene and dicyclopentadiene.

Specific examples of such polar solvents include tetrahydrofuran, tetramethylethylenediamine, trimethylamine, triethylamine, ethyl ether, tetrahydrofuran,
Examples include dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, dipiperidinoethane, and the like. Methyllithium, ethyllithium, n-propyllithium, isopyllithium, n-butyllithium, 5ec-ethyllithium, isobutyllithicum, tert-butyllithium, n-pentyllithium, n-hexyl as l-i type catalysts. lithium,
Examples include trimethylsilyllithium. 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, 1-butene, 1,3-butadiene, cyclopentene, 13-pentadiene, 1-hexene, 2-hexenecyclohexene, 1
- Suitable for hydrogenation of methylcyclohexene, styrene, 1 to octene, etc.

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

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

Conjugated dienes used in the production of such conjugated diene polymers generally include conjugated dienes having from 4 to about 12 carbon atoms, specific examples include 1,3-
Butadiene, isoprene, 2,3-dimethyl-1,3-
Butadiene, 1,3-pentadiene, 2-methyl-1,
3-pentadiene, 1,3-hexyldiene, 4,5-diethyl-1,3-octadiene, 3-butyl-1,3-
Examples include octadiene. 1,3-butadiene and isoprene are particularly preferred from soils that can be industrially advantageously developed and provide elastic bodies with excellent physical properties.

In addition, as the olefin monomer copolymerizable with at least 2 types of conjugated dienes, vinyl-substituted aromatic hydrocarbons are particularly preferred. In order to achieve the effects of the present invention by selectively hydrogenating only the unsaturated double bonds of the conjugated diene unit and to obtain an industrially useful and valuable elastomer or thermoplastic elastomer, Of particular interest are copolymers of conjugated dienes and vinyl-substituted aromatic hydrocarbons. Specific examples of vinyl-substituted aromatic hydrocarbons that can be used include styrene, t-butylstyrene, α-methylstyrene, p-methylstyrene, divinylbenvin, 1,1-sifenylethylene, N,N
-dimethyl-p-amineethylstyrene, N, N'
-diethyl-p-aminoethylstyrene, etc., 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 industrial value.

Among such copolymers, block copolymers provide hydrogenated polymers that are industrially most useful as thermoplastic elastomers; Coalescence 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. 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 not a single ether, but a mixture.

Aromatic hydrocarbons such as benzine, toluene, xylene, and ethylbenpine can also be used provided that aromatic double bonds are not hydrogenated under the selected hydrogenation reaction conditions.

The hydrogenation reaction of the present invention is carried out in the following manner: - The hydrogenated product solution is maintained at a predetermined temperature in a hydrogen or inert atmosphere in the membrane, 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 gas.

It is necessary to handle the catalyst component (8) under said 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 the catalyst components (A) and (B) 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 the catalyst components are mixed in advance or when the catalyst components are added to the hydrogenation reactor, it is most preferable to carry out the reaction under a hydrogen atmosphere. When catalyst component (A) and catalyst component (B) are mixed in advance and used, they are prepared at a temperature of 30°C to 100°C, preferably at a temperature of -10°C to 50°C immediately before the hydrogenation reaction. However, if it is stored under a hydrogen atmosphere or an inert atmosphere, it can be used without changing its substantial hydrogenation activity even at room temperature for about one week.

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 (8) to the number of metal moles of catalyst component (A) (below) 1 etal (
B)/) Fetal (A) molar ratio) is in the range of about 20 or less. Metal (B)/Metal (A) seven ratio
Although it is possible to carry out a regular hydrogenation reaction in 〇, it requires higher temperature and higher pressure conditions, and Metal (B)
, /'When the molar ratio of Metal (A) 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 lead to unnecessary side reactions. I don't like it.

Hetal (B)/Metal (A) molar ratio -〇, a range of 5 to 10 is most suitable for significantly improving hydrogenation activity.

In the case of a living polymer obtained by hydrogenated anionic polymerization, this Metal(B)/Metal(
A) In order to achieve the molar ratio, it is preferable to deactivate with compounds having various active hydrogens and halogens. Compounds having such active hydrogen include water and methanol, ethanol, n-propanol, n-butanol, 5ec-butanol, t-butanol, 1-pentanol, 2-pentanol, 3-pentanol, 1-hexanol, 2 -hexanol, 3-hexanol, 1-heptatool, 2
- heptal, 3-heptatool, 4-heptatool,
Alcohols such as ophthal, nofnol, decanol, undecyl alcohol, lauryl alcohol, allyl alcohol, cyclopentanol, cyclopentanol, hensyl alcohol, phenol, O-cresol, m-
Cresol, p-cresol, p-allylphenol,
2,6-cy↑-butyl-p-cresol, xylenol, dihydroanthraquinone, dihydroxycoumarin,
Examples include phenols such as 1-hydroxyanthraquinone, m-hydroxybenzyl alcohol, resorcinol, and leukoaralin.

In addition, organic carboxylic acids such as acetic acid, prodionic acid, butyric acid, isobutyric acid, pentanoic acid, hexanoic acid, heptanoic acid, decanoic acid, myristic acid, stearic acid, hebenic acid, benzoic acid, methylbenzoic acid, etc. can be mentioned.

In addition, compounds containing halogen include pencil chloride, trimethylsilyl chloride (bromide), t-butyl chloride (bromide), methyl chloride (bromide), ethyl chloride (bromide), propyrochloride 1 (but), n-7 Fulk [J-Light (
bromide) etc., 4 catalytic acids (C
) is added, the amount of the catalyst component (C) added is preferably 10 to 500 in weight i ratio to the catalyst of the catalyst component (A). If it is smaller than 10, the effect of fixing the storage capacity and reducing the amount of catalyst becomes small. Even if it exceeds 500, the hydrogenation activity is good, but if it is a hydrogenated product or a polymer, it is difficult to separate the hydrogenated polymer from the catalyst (C) component, so in some cases the physical properties etc. It's having an impact.

Hydrogenated product or olefinically unsaturated double bond gold-containing polymer, whether the side chain olefinically unsaturated double bond gold content, the total olefinically unsaturated double bond gold content, or the total olefin If it is 0.3 to 1 with respect to the unsaturated double bond,
One part of this may be used as the (C) catalyst component, or another part (C)
It may be used in combination with other ingredients.

The amount of catalyst added is 0.005 to 20 per 100g of hydrogenated material.
Millimoles are sufficient. If the amount of added #Fl is within this range, it is possible to preferentially (or hydrogenate) the olefinic unsaturated double bonds of the hydrogenated product, and the hydrogenation of the aromatic@nuclear 2,000 bonds in the copolymer is substantially Extremely high hydrogenation selectivity is achieved because the hydrogenation reaction does not occur.Although the hydrogenation reaction is possible even if the amount exceeds 20 ml, using more catalyst than necessary will result in a wasteful reaction, and the Moreover, under the selected conditions, the preferred amount of catalyst added to consistently hydrogenate the unsaturated double bonds in the conjugated diene units of the polymer is It is 0.05 to 5 mmol per 100!iF of coalescence.

The hydrogenation reaction of the present invention is carried out using elemental hydrogen, more preferably introduced in gaseous form into the hydrogenate solution. It is more preferable that the hydrogenation reaction is carried out under stirring, so that the introduced hydrogen can be brought into contact with the hydrogenated substance quickly enough. The hydrogenation reaction is generally carried out at a temperature range of 0 to 200°C. Below 0°C, the activity of the catalyst decreases and the hydrogenation rate slows down, requiring a large amount of catalyst, which is not economical, and also
Temperatures exceeding 00'C are not preferred because side reactions, decomposition, and gelation are likely to occur together, and hydrogenation of the aromatic nucleus portion is also likely to occur, resulting in a decrease in hydrogenation selectivity.

The temperature is generally preferably in the range of 40 to 160°C.

The size of the hydrogen used in the hydrogenation reaction is 1.~3 in 100
- d is preferable. If the pressure is less than 1Kg7cm', the hydrogenation rate will slow down and virtually reach a plateau, making it difficult to increase the hydrogenation rate.If the pressure exceeds 100Kg, 7cm', the hydrogenation reaction will occur at the same time as the back pressure. It is not preferable because it is essentially meaningless and causes unnecessary side reactions and gelation.

A more preferable hydrogenation pressure is 2 to 308 g/'cIi, but the most optimal hydrogen pressure is selected in correlation with the amount of catalyst added, etc. Substantially, as the preferred amount of catalyst becomes smaller, the hydrogen repulsion becomes higher pressure. It is preferable to choose one side and implement it.

Furthermore, since the hydrogenation rate of low molecular olefins is faster than that of polymers, milder conditions are selected compared to those for 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, if necessary, residual catalyst can be removed from a polymer solution subjected to the hydrogenation reaction according to the method of the present invention, and the hydrogenated polymer can be easily isolated from the solution. for example,
The reaction solution after hydrogenation (a method in which the polymer is precipitated and recovered by adding a polar solvent such as acetone or alcohol that is a poor solvent for the hydrogenated polymer, the reaction solution is stirred and poured into boiling water, and then distilled together with the solvent) This can be carried out by a method of recovering, or a method of 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 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.

(Effects of the Invention) As described above, the method of the present invention makes it possible to efficiently hydrogenate olefinically unsaturated double bonds. By hydrogenating under mild conditions, it is possible to extremely selectively hydrogenate the unsaturated double bond in the center of the conjugated diene of a copolymer of a conjugated diene and a hinyl-substituted aromatic hydrocarbon. In addition, compared to the conventional catalyst using a metallocene compound having a cyclopentadienyl ring, the catalyst is less deactivated by high temperature, the hydrogenation rate increases due to temperature increase, and the polymer solution of the hydrogenated substance is reduced. It was possible to reduce the viscosity of the solution and increase the degree of the solution, resulting in a significant increase in productivity.

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 it with other elastic bodies or resins, making it extremely useful industrially.

[Examples] The present invention will be explained in detail with reference to Examples below, but the present invention is not limited thereto.

Synthesis examples of the bentame F-lucychlorobentazine and meta-conductor conductors and each polymer used in the examples are shown in the following reference examples.

Reference Example 1 Pentamethylcyclopentadiene beam was synthesized with reference to the method of Devri (J, Org, Che
M, 25 (1960) 1838) and 95% of Aldocs 1) were distilled under reduced pressure and used (5
8-60°C/'13mm [1g> A well-dried three-necked flask equipped with a stirrer was ice-cooled, and 50g (0,370mol> of pentamethylcyclopentadiene and 900g of dried giraffe) were added thereto, and then 15 A hexane solution of 2487% butyllithium (
0,408 m01> The mixture was added dropwise with stirring over about 15 minutes.

After stirring for 1 hour at room temperature, the concentration of pentamethylcyclopentadienyllithium determined by the Gilman method was 0.332.
mo1. #Met. Bequinone was distilled off by reducing the pressure of this solution, and dry 1,2-dimethoxyethane was added to adjust the concentration to 1.05 mol/1.

After replacing the dried 2g7f-1 ~ crepe with dry l\lium for 11 minutes, titanium tetrachloride 40s7 (0,21
0 mol), 1.2-lame 1-xyTtan 2007 were added. Pentamethylcyclopentadienyllithium (
A solution of 1.2-lame 1 to xyethane (400 rn1) of 1.2-lame 1-xyethane (42 nof) was added at a temperature of -20° C. and stirred for 40 minutes.

After 1 hour, the temperature was returned to room temperature, solid content was filtered out in the air, and the filtrate was dried in an evaporator to obtain dark brown crystals. Bis(
The yield of titanium dichlorite (pentamethylcyclopentadienyl) was 85%. It was purified by recrystallization in dichloromethane and dried under vacuum at 35°C for 24 hours.

Reference Example 2 28 g (0,072 m
1.2- of 300d in 1g autoclave
(partial suspension dissolved in dimethoxyethane), −
Phenyllithium (0,1511101') at 20°C
A diethyl ether solution (200 rnl) of Crystals were obtained.The yield of his(pentamethylcyclopentagenyl)diphenyl analyzed by liquid chromatography was 96%.

Reference Example 3 The same procedure as Reference Example 2 was carried out except that p-methylphenyl(tolyl>lithium was used instead of phenyllithium in Reference Example 2.Bis(pentamethylcyclopentadienyl)ditolyl was purified by liquid chromatography. The yield was found to be 95%.

Reference example 4 Cyclohexane 5007.1 in an autoclave of 21
, 3-butadiene mono? -100 g and 0.05 g of n-butyllithium were added, and polymerization was carried out at 60°C for 3 hours with stirring. Next, 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 one has 11 1,2-vinyl bonds.
%, and the number average molecular weight measured by GPC was 15 hours.

Reference Example 5 An isoprene polymer was synthesized in exactly the same manner as in Reference Example 4, except that isoprene was used instead of 1.3-butadiene. This product had a 1,2-vinyl bond of 10% and a number average molecular weight of about 150,000.

Reference Example 6 400 g of cyclohexane, 707 g of 1,3-butadiene monomer, 30 g of styrene monomer, 0.039 g of n-butyllithium, and 0.97 g of tetrahydrofuran were simultaneously added to an autoclave and polymerized at 40° C. for 2 hours. Next, 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 was a completely random copolymer of butadiene/styrene having a 1,2-vinyl bond content of butadiene units of 50% and a weight average molecular weight of 200,000.

Reference Example 7 400 y of cyclohexane, 159 y of styrene monomer and 0.119 y of n-butyl lithium were placed in an autoclave, mixed at 60"C for 3 hours, and then 1,3-butylene chloride was added. 70g was added and the mixture was heated at 60°C for 3 hours.

Finally, 15g of styrene monomer was added and
The IR deal was made. 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 content of 1,2-vinyl bound metal of 12% (8% in terms of the total polymer), and a number average molecular weight of approximately 60,000. It was a styrene-butadiene-styrene type block copolymer.

Reference Example 8 In Reference Example 7, except that 35 times the molar amount of tetrahydrofuran was added to n-butyl lithium, the same method was used to prepare a compound with a bound styrene content of 30%, a block styrene content of 24%, and a 1,2-vinyl butadiene unit. Combined metal 1i
A styrene-butadiene-styrene type block copolymer having a number average molecular weight of 39% (23% in terms of total polymer) and a number average molecular weight of about 60,000 was synthesized.

Reference example 9 During autoclaving, tsuku[]l\kilfukiooog, 1
3-Butamonone seven? -100'j, n-butyl lithium [
The molar ratio of cum 0.559 and tetrahydrofuran is n
-B LJ L l / -r HF = 1/40 (
7) AiLa treatment, polymerization at 70°C for 45 minutes, then adding styrene monomer 1509 for 60 minutes, then 1.3
-butadiene-shitsuma-eoo g was added for 150 minutes,
Finally, 150 g of styrene monomer was added and polymerized for 60 minutes to synthesize a 10-butadiene-styrene-butadiene-styrene type copolymer. After deactivating and precipitating this living polymer solution in a large amount of methanol,
Vacuum drying was performed at 0°C for 50 hours. This is a block copolymer with a bound styrene content of 30%, a block styrene content of 28%, a 1,2-vinyl bound gold content of butadiene units of 35% (25% in terms of the total polymer), and a number average molecular weight of approximately 120,000. It was a combination.

Reference Example 10 A butadiene-styrene-butadiene-styrene type living block co-assembly was prepared in exactly the same manner as in Reference Example 1. This product has 0.83 ml of pink lithium per 1007 polymer, and when it was partially separated and analyzed, it contained 30% bound styrene and 30% blocked styrene.
27%, 1,2-vinyl bond metal content 3
4% (total polymer conversion rate: 24%), and the number average molecular weight was approximately 120,000.

Example 1 1-hexene and cyclohexene were diluted with cyclohexene, adjusted to 8 degrees and 15%, and subjected to a hydrogenation reaction.

In a sufficiently dry autoclave with a capacity of 2 g and equipped with a stirrer,
After 1000 g of the above olefin compound solution was added and degassed under reduced pressure, the mixture was replaced with hydrogen and maintained at 60'C with stirring. Then, 100 d of a cyclohexane solution containing 1 mmol of bis(pentamethylcyclopentadienyl) titanium dichlorite prepared in Reference Example 1 as the catalyst component (A);
A catalyst solution (li/T! molar ratio -
2) Prepare the entire ψ from 71-1 to crepe medium, 5. ON
After supplying the dried casseous aqueous system of crA and carrying out hydrogenation for 2 hours with stirring, the reaction solution was returned to room temperature and normal pressure, and the hydrogenation rate was determined by Kaschroma]-Granoy analysis. Ta.

Show results artificially.

Example 2 Example 1 Hiss (pentamethylcyclopentagenyl)
The same procedure was carried out except that instead of using titanium dichloride, bis(pentamethylsif[]pentadienyl)ditanir-cumsif-nil synthesized in Reference Example 2 was used.

Show results artificially.

Example 3 Example 1 Bis(pentamethylcyclopentadienyl)
The same procedure was carried out except that instead of using titanium cyclolite, bis(pentamethylcyclopentagenyl)titanium]-lyl synthesized in Reference Example 3 was used.

The results are shown in Table f.

Table D Examples 4 to 10 The various polymers obtained in Reference Examples 4 to 10 were diluted with purified and dried cyclohexane to adjust the polymer concentration to 8% and 5% by weight, and then subjected to a hydrogenation reaction. In addition, the Ping polymer solution obtained in Reference Example 10 was diluted with purified and dried cyclohexane,
Living polymer yA was adjusted to 5% by weight and subjected to hydrogenation reaction.

In a sufficiently dry autoclave with a capacity of 2J and equipped with a stirrer,
The above various polymer solutions or lipping polymer solutions ioo
og, degassed under reduced pressure, replaced with hydrogen, and heated to 60'C with stirring.
was held at

Then, 50 ml of a cyclohexane solution containing 12 milliliters of his(penmethylschiff[l pentagenyl) titanium dichloride phytoO as the catalyst component FA) and the catalyst component (FA) were added.
8) A catalyst solution (Mg /Ti molar ratio -4) was charged into an autoclave, 5.0 ffy/Ci of dry gaseous hydrogen was supplied, and a hydrogenation reaction was carried out for 2 hours under stirring. The reaction solution was returned to room temperature and pressure, taken out from the odocrape, a large amount of methanol was added to precipitate the polymer, and the mixture was filtered and dried to obtain a white hydrogenated polymer. The hydrogenation rate of the obtained hydrogenated polymer was determined from the infrared absorption spectrum (details on how to determine the hydrogenation rate are given in JP-A-59-133203 e) Table 1
It was shown to.

(Leaving space below) Examples 11 to 19 The 1-T-1-Y-L-But-C-Brene type 10-TSU copolymer synthesized in Reference Example 9 was diluted with purified and dried cyclohekirin to give 5116, This solution 1000
Sj was put into an autoclave and hydrogenated in the same manner as in Example 4 under various conditions shown in Table 11M. The results are shown in Table ■.

Examples 20 to 22 The butadiene-styrene-phtadiene-styrene type 10-block copolymer synthesized in Reference Example 9 was diluted with purified and dried cyclohexane and concentrated to 5% by weight, and 1000 g of this solution was prepared.
was charged into an autoclave, the catalyst component (A) was bis(pentamethylcyclopentadienyl)diphenyl, the catalyst component (B) was n-butyllithium, and hydrogenation was carried out under various conditions shown in Table IV.

The results are shown in Table IV.

Comparative Example 1 The same procedure as Example 20 was carried out except that the catalyst component (A) was bis(cyclopentadienyl)diphenyl. The results are shown in Table IV.

Comparative Example 2 The same procedure as in Example 22 was performed except that the catalyst component (A) was 8-his(cyclopencdinyl-1-yl)ditolyl. The results are shown in Table 1v.

(Left below)

Claims (1)

[Claims] 1. An olefinically unsaturated double bond-containing compound in an inert organic solvent, (A) At least one metallocene compound represented by the following general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (However, R is a methyl group, and R^1 and R^2 are C_1
~C_1_2 represents a group selected from a 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. Further, M represents a metal selected from Ti, Zr, and Hf. ) and (B) olefinically unsaturated double bonds in the compound by contacting with hydrogen in the presence of a catalyst comprising at least one of lithium, sodium, potassium, aluminum, zinc or magnesium-containing compounds having reducing ability. A method for hydrogenating olefins, the method comprising hydrogenating olefins. 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_5 (CH_3)_5}_2TiCl_
2 and (B) n-butyllithium and/or sec-
The hydrogenation method according to claim 1, wherein the hydrogenation method is butyllithium and/or triethylaluminum and/or ethylmagnesium chloride.