JPH0841081A - New titanocene compound, catalyst composition for hydrogenating olefin compound and method for hydrogenating olefin compound using the same catalyst composition - Google Patents

Abstract

PURPOSE:To obtain a new titanocene compound which is a component of a catalyst useful for selectively hydrogenating an olefinic unsaturated double bond of a conjugated diene-based polymer or a copolymer of a conjugated diene with a vinylaromatic hydrocarbon and excellent in storage stability, etc. CONSTITUTION:A titanocene compound of formula I (R<1> and R<2> are each H or 1-12C hydrocarbon, wnth the provnso that all of R<1> and R<2> is not H or 1-12C hydrocarbon; R<3> and R<4> are each H or 1-4C hydrocarbon, with the proviso that all of R<3> and R<4> is not a hydrocarbon), e.g. bis(iota<5>-methylcyclopentadienyl)di- p-tolyltitanium. This compound of formula I is obtained by reacting, e.g. a quadrivalent titanocenehalogen compound containing an alkyl-substituted cyclopentadienyl group with an aryllithium. This catalyst composition can be obtained from (A) one or more kinds of titanocene compounds of formula II (R<5> and R<6> are each H, a 1-12C hydrocarbon, an aryloxy, etc.) and (B) a reducing agent comprising a compound containing one or more atoms of Li, Na, K, etc.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a catalyst composition for hydrogenating an olefin compound and an olefin compound, preferably a conjugated diene polymer, or a copolymer of a conjugated diene and a vinyl aromatic hydrocarbon using the catalyst composition. The present invention relates to a method for selectively hydrogenating an olefinically unsaturated double bond in a polymer and a novel titanocene compound newly created among titanocene compounds as one component of the catalyst composition.

[0002]

2. Description of the Related Art As a hydrogenation catalyst for a compound having an olefinically unsaturated double bond, a heterogeneous catalyst and a homogeneous catalyst are generally known. The former heterogeneous catalyst is widely used industrially, but is generally less active than the homogeneous catalyst, and a large amount of catalyst is required to carry out the desired hydrogenation reaction. It will be uneconomical because it is exposed On the other hand, the latter homogeneous catalyst has a characteristic that it can be hydrogenated at a lower temperature and a lower pressure, because the hydrogenation reaction usually proceeds in a homogeneous system, so the activity is high and the amount of the catalyst used is small compared to a heterogeneous system. On the other hand, the catalyst preparation is complicated, the stability of the catalyst itself is not sufficient, the reproducibility is poor, and undesired side reactions are likely to occur simultaneously. In addition, when hydrogenating an alkyl-substituted olefinically unsaturated double bond having steric hindrance, sufficient hydrogenation activity has not been obtained. Therefore, under the present circumstances, there is a strong demand for the development of a hydrogenation catalyst which has high activity and is easy to handle.

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

The present applicants have already combined a specific titanocene compound with an alkyllithium to hydrogenate an olefin compound (Japanese Patent Laid-Open Nos. 61-33132 and 1-53851), metallocene compounds and organic compounds. A method of hydrogenating an olefinically unsaturated (co) polymer in combination with aluminum, zinc and magnesium (Japanese Patent Laid-Open No. Sho 61-61).
No. 28507, JP-A-62-209103), a method of hydrogenating a living polymer containing an olefinically unsaturated group with a combination of a specific titanocene compound and an alkyllithium (JP-A-61-47706, JP-A-61-47706). Kaisho 6
No. 3-5402). However, although these methods are highly active, it is difficult to handle the hydrogenated catalyst, and long-term storage stability is also difficult.

On the other hand, a method of hydrogenating an olefinic double bond in a polymer containing an olefinically unsaturated double bond with a combination of a specific titanocene compound and alkoxylithium (JP-A-1-275605) is disclosed. ing.
This method further requires an expensive organometallic compound other than alkoxylithium as a reducing agent. Further, a method of hydrogenating an olefinic double bond in an olefinic unsaturated double bond-containing polymer with a combination of a specific titanocene compound, an olefin compound and a reducing agent (JP-A-2-17253).
No. 7) is disclosed. Although this indicates storage stability and activity reproducibility as effects, long-term storage stability for one month or more is not sufficient.

Since the titanocene compound, which is the main catalyst of these inventions, is basically the same as the conventionally known catalysts invented by the present applicants, there is a limit to the heat resistance of the catalysts and the use conditions are limited. There was a drawback. Therefore, in order to solve these problems, the present inventors have combined a reducing agent with a metallocene compound having a pentamethylcycloentadienyl group in which all five hydrogens of a cyclopentadienyl group have been replaced with methyl groups. A method for hydrogenating an olefin compound was filed (Japanese Patent Laid-Open No. 4-96904). Although the heat resistance of the catalyst was improved by this method, the hydrogenation rate was slow, and particularly under mild conditions, the hydrogenation rate was considerably lower than that of conventional titanocene catalysts, and the long-term storage stability of the catalyst was also insufficient. , Further improvement was desired.

[0007]

DISCLOSURE OF THE INVENTION The present invention is stable and easy to handle, has excellent heat resistance, and has the advantage of quantitative hydrogenation with a very small amount of hydrogenation of an olefin compound in a wide temperature range, in addition to several months. An object of the present invention is to find a method for obtaining an ultra-high activity hydrogenated catalyst composition that can withstand long-term storage and exhibits high activity with good reproducibility during a hydrogenation reaction, and hydrogenate an olefin compound using the catalyst composition.

[0008]

Means and Actions for Solving the Problems
An olefin compound which is brought into contact with hydrogen in the presence of a catalyst composition composed of (A) a specific titanocene compound having an alkyl-substituted cyclopentadienyl group and (B) a specific metal compound reducing agent having a reducing ability. The heat resistance of the catalyst is significantly improved when hydrogenating the olefinic unsaturated double bond in the catalyst, and it exhibits high activity over a wide temperature range. Furthermore, coexistence with a specific additive stabilizes long-term activity. It is based on the surprising fact that the sex is also outstanding. That is, the present invention provides [1] a titanocene compound represented by the following general formula (Formula 5).

[0009]

Embedded image

(However, R ¹ and R ² are hydrogen, C _{1 to} C ₁₂
And R ¹ and R ² may be the same or different. However, the case where R ¹ and R ² are all hydrogen or all are C _{1 to} C ₁₂ hydrocarbon groups is excluded. R ³ and R ⁴ represent hydrogen or a group selected from C _{1 to} C ₄ hydrocarbon groups, and R ³ and R ⁴ may be the same or different. Provided that R ³ and R ⁴ are all hydrocarbon groups) and [2] (A) at least one of the titanocene compounds represented by the following general formula (Formula 6)

[0011]

[Chemical 6]

(However, R ⁵ and R ⁶ are hydrogen, C _{1 to} C ₁₂
Represents a group selected from a hydrocarbon group, an aryloxy group, an alkoxy group, a halogen group and a carbonyl group,
R ⁵ and R ⁶ may be the same or different. R ¹ , R ²
Represents hydrogen or a group selected from C _{1 to} C ₁₂ hydrocarbon groups, and R ¹ and R ² may be the same or different. However,
Except when R ¹ and R ² are all hydrogen or all C _{1 to} C ₁₂ hydrocarbon groups. (B) A catalyst composition for hydrogenating an olefin compound composed of at least one reducing agent selected from compounds containing at least one element of Li, Na, K, Mg, Zn, Al and Ca. And

[3] The catalyst composition is the above-mentioned component (A),
A catalyst composition for hydrogenating an olefin compound, which comprises a component (B) and the following component (C). (C) The ratio of the amount of olefinically unsaturated double bonds in the side chain to the total amount of olefinically unsaturated double bonds is 0.3 to 1
Is an olefinically unsaturated double bond-containing polymer. And

[4] Hydrogen of an olefin compound in which the catalyst composition contains the following components (A) and (B) or components (A), (B) and (C) and the following component (D). Additive catalyst composition, (D) alcohol compound, ether compound, thioether compound, ketone compound, sulfoxide compound, carboxylic acid compound, carboxylic acid ester compound, aldehyde compound, lactone compound, amine compound, amide compound, nitrile compound, epoxy compound And at least one polar compound selected from the group of oxime compounds. And

[5] When the olefinically unsaturated double bond-containing compound is brought into contact with hydrogen in an inert organic solvent to hydrogenate the olefinically unsaturated double bond in the compound, the above (A) is used. (B) or (A) (B) (C) or (A) (B) (D) or (A) (B) (C) (D) in the presence of a catalyst composition Of hydrogenating an olefin compound comprising: [6] A method for hydrogenating an olefin compound, wherein a preferred olefin compound is a conjugated diene polymer or a polymer of a conjugated diene and a vinyl aromatic hydrocarbon.

At least one of the usual titanocene compounds having a cyclopentadienyl group which is not substituted with an alkyl group (A ') and a compound (B) having a reducing power, and (A') and (B) having a side chain. Conjugated diene-based polymer by combining with an olefinically unsaturated double bond-containing polymer (C) having an olefinic unsaturated double bond in a specific ratio or more, or a co-weight of a conjugated diene and a vinyl aromatic hydrocarbon A metallocene compound having a pentamethylcyclopentadienyl group (A) having a pentamethylcyclopentadienyl group with improved heat resistance, which is obtained by selectively hydrogenating an olefinically unsaturated double bond of the polymer (JP-A-4-96905). The method of hydrogenating an unsaturated double bond of an olefin compound using a catalyst composition composed of ") and (B) (JP-A-4-96904) is by the present inventors. It is gun.

The present inventors further provide a hydrogenation catalyst which improves the heat resistance of this prior application olefin hydrogenation catalyst, does not decrease the speed under conventional conditions, and has excellent storage stability for several months. As a result of diligent studies, (A) a titanocene compound having an alkyl group-substituted cyclopentadienyl group having a specific structure (excluding 5 substituents) and (B) at least one specific element are contained. The catalyst composition composed of at least one reducing agent selected from compounds is an olefin compound, preferably a conjugated diene-based polymer or an olefinically unsaturated double bond of a conjugated diene-vinyl aromatic hydrocarbon copolymer. Has been found to selectively and highly hydrogenate hydrogen in a wide temperature range with an unnecessary level of deashing, and (A), (B) and (C) or (A) B) and (D) or (A) (B)
The inventors have found that the combination of (C) and at least one compound (D) selected from specific alcohol, ketone, aldehyde compounds and the like is also excellent in activity reproducibility and long-term storage stability, and completes the present invention. It came to.

The titanocene compound according to claim 1 of the present invention is a novel compound synthesized by the present inventors. The compound can be synthesized, for example, by reacting a tetravalent titanocene halogen compound having a cyclopentadienyl group having an alkyl substituent with aryllithium. Confirmation of synthesized compounds is ¹
It can be confirmed by 1 H-NMR and MS spectrum. This compound can be used as a hydrogenation catalyst and is also useful as a polymerization catalyst for olefins and dienes. The hydrogenation catalyst component (A) according to the present invention is represented by the following general formula (Formula 7).

[0019]

[Chemical 7]

(However, R ⁵ and R ⁶ are hydrogen, C _{1 to} C ₁₂
Represents a group selected from a hydrocarbon group, an aryloxy group, an alkoxy group, a halogen group and a carbonyl group,
R ⁵ and R ⁶ may be the same or different. R ¹ , R ²
Represents hydrogen or a group selected from C _{1 to} C ₁₂ hydrocarbon groups, and R ¹ and R ² may be the same or different. However,
Except when R ¹ and R ² are all hydrogen or all C _{1 to} C ₁₂ hydrocarbon groups. ) As the C _{1 to} C ₁₂ hydrocarbon groups of R ¹ and R ² , for example, substituents represented by the following general formula (Formula 8) are also included.

[0021]

Embedded image

(Wherein R ⁷ to R ⁹ represent hydrogen or a C ₁ to C ₄ alkyl hydrocarbon group, and at least one of R ⁷ to R ⁹ is hydrogen, and n = 0 or 1) The compound having an alkyl hydrocarbon group in the ortho position with respect to the central metal is active, but is not preferable because it is difficult to synthesize. The novel titanocene compound of claim 1 can also be used as a part of the catalyst component (A) of claim 2 or the following.

Specific examples of the catalyst component (A) include bis (η ⁵ -methylcyclopentadienyl) titanium dihydride, bis (η ⁵ -1,3-dimethylcyclopentadienyl) titanium dihydride and bis ( η ⁵ -Ethylcyclopentadienyl) titanium dihydride, bis (η
⁵ -propylcyclopentadienyl) titanium dihydride, bis (η ⁵ -n-butylcyclopentadienyl)
Titanium dihydride, bis (η ⁵ -methylcyclopentadienyl) titanium dimethyl, bis (η ⁵ -1,3
-Dimethylcyclopentadienyl) titanium dimethyl, bis (η ⁵ -ethylcyclopentadienyl) titanium dimethyl, bis (η ⁵ -propylcyclopentadienyl) titanium dimethyl, bis (η ⁵ -n-butylcyclopentadienyl) ) Titanium dimethyl, bis (η ⁵
-Methylcyclopentadienyl) titanium diethyl,
Bis (eta ^{5-1,3-dimethyl-cyclopentadienyl)}
Titanium diethyl, bis (η ⁵ -ethylcyclopentadienyl) titanium diethyl, bis (η ⁵ -propylcyclopentadienyl) titanium diethyl,

[0024] bis (eta ^5-n-butyl cyclopentadienyl) titanium diethyl, bis (eta ⁵ - methyl cyclopentadienyl) titanium di -sec- butyl, bis (eta ^{5-1,3-dimethyl-cyclopentadienyl} (Enyl) titanium di-sec-butyl, bis (η ⁵ -ethylcyclopentadienyl) titanium di-sec-butyl, bis (η ⁵ -propylcyclopentadienyl) titanium di-sec-butyl, bis (η ^5- n-butylcyclopentadienyl) titanium di-sec-butyl, bis (η
⁵ - cyclopentadienyl) titanium dihexyl, bis (eta ^{5-1,3-dimethyl-cyclopentadienyl)} titanium dihexyl, bis (eta ⁵ - ethyl cyclopentadienyl) titanium dihexyl, bis (eta ⁵ -
Propylcyclopentadienyl) titanium dihexyl, bis (η ⁵ -n-butylcyclopentadienyl) titanium dihexyl, bis (η ⁵ -methylcyclopentadienyl) titanium dioctyl,

[0025] bis (eta ^{5-1,3-dimethyl-cyclopentadienyl)} titanium dioctyl, bis (eta ⁵ - ethyl cyclopentadienyl) titanium dioctyl, bis (eta ⁵ - propyl cyclopentadienyl) titanium dioctyl, bis (Η ⁵ -n-butylcyclopentadienyl) titanium dioctyl, bis (η ⁵ -methylcyclopentadienyl) titanium dimethoxide, bis (η ⁵
-1,3-Dimethylcyclopentadienyl) titanium dimethoxide, bis (η ⁵ -ethylcyclopentadienyl) titanium dimethoxide, bis (η ⁵ -propylcyclopentadienyl) titanium dimethoxide, bis (η ⁵ − n- butylcyclopentadienyl) titanium dimethoxide, bis (eta ⁵ - methyl cyclopentadienyl) titanium diethoxide, bis (eta ^{5-1,3-dimethyl-cyclopentadienyl)} titanium diethoxide, bis ( η ⁵ -Ethylcyclopentadienyl) titanium diethoxide, bis (η ⁵ -propylcyclopentadienyl) titanium diethoxide, bis (η ⁵ -n-
Butylcyclopentadienyl) titanium diethoxide, bis (η ⁵ -methylcyclopentadienyl) titanium dipropoxide,

Bis (η ⁵ -dimethylcyclopentadienyl) titanium dipropoxide, bis (η ⁵ -ethylcyclopentadienyl) titanium dipropoxide, bis (η ⁵ -propylcyclopentadienyl) titanium dipropoxide , bis (eta ^5-n-butyl cyclopentadienyl) titanium dipropoxide Sid, bis (eta ⁵ - methyl cyclopentadienyl) titanium dibutoxide, bis (eta ^{5-1,3-dimethyl-cyclopentadienyl)} titanium Jibutokishido, bis (eta ⁵ - ethyl cyclopentadienyl) titanium dibutoxide, bis (eta ⁵ - propyl cyclopentadienyl) titanium jib preparative propoxide, bis (eta ^5-n-butyl cyclopentadienyl) titanium jib topo Kishido, bis (eta ⁵ - methylcyclopentadienyl) Chitaniu Diphenyl, bis (eta ⁵ -
1,3-methylcyclopentadienyl) titanium diphenyl, bis (η ⁵ -ethylcyclopentadienyl) titanium diphenyl, bis (η ⁵ -propylcyclopentadienyl) titanium diphenyl, bis (η ⁵ -n-
Butylcyclopentadienyl) titanium diphenyl,
Bis (η ⁵ -methylcyclopentadienyl) titanium di (m-tolyl),

[0027] bis (eta ^{5-1,3-methylcyclopentadienyl)} titanium di (m-tolyl), bis (eta ⁵ -
Ethylcyclopentadienyl) titanium di (m-tolyl), bis (η ⁵ -propylcyclopentadienyl) titanium di (m-tolyl), bis (η ⁵ -n-butylcyclopentadienyl) titanium di (m -Tolyl), bis (η ⁵ -methylcyclopentadienyl) titanium di (p-tolyl), bis (η ⁵ -1,3-methylcyclopentadienyl) titanium di (p-tolyl), bis (η
⁵ -ethylcyclopentadienyl) titanium di (p-
Tolyl), bis (η ⁵ -propylcyclopentadienyl) titanium di (p-tolyl), bis (η ⁵ -n-butylcyclopentadienyl) titanium di (p-tolyl), bis (η ⁵ -methylcyclo) Pentadienyl) titanium di (m, p-xylyl), bis (η ⁵ -1,3-
Dimethylcyclopentadienyl) titanium di (m, p
-Xylyl), bis (η ⁵ -ethylcyclopentadienyl) titanium di (m, p-xylyl),

Bis (η ⁵ -propylcyclopentadienyl) titanium di (m, p-xylyl), bis (η ⁵ −
n-butylcyclopentadienyl) titanium di (m,
p-xylyl), bis (η ⁵ -methylcyclopentadienyl) titanium di (4-ethylphenyl), bis (η
⁵ -1,3-dimethyl-cyclopentadienyl) titanium di (4-ethylphenyl) bis (eta ⁵ - ethyl cyclopentadienyl) titanium di (4-ethylphenyl) bis (eta ⁵ - propyl cyclopentadienyl (Enyl) titanium di (4-ethylphenyl), bis (η ⁵ -n-
Butylcyclopentadienyl) titanium di (4-ethylphenyl), bis (η ⁵ -methylcyclopentadienyl) titanium di (4-hexylphenyl), bis (η
⁵ -1,3-dimethyl-cyclopentadienyl) titanium di (4-hexyl-phenyl)

Bis (η ⁵ -ethylcyclopentadienyl) titanium di (4-hexylphenyl), bis (η
⁵ -propylcyclopentadienyl) titanium di (4
- hexyl phenyl), bis (eta ^5-n-butyl cyclopentadienyl) titanium di (4-hexyl-phenyl), bis (eta ⁵ - methyl cyclopentadienyl) Titanium diphenoxide, bis (eta ^5-1,3 - dimethyl cyclopentadienyl) titanium diphenoxide, bis (eta ⁵ - ethyl cyclopentadienyl) titanium diphenoxide, bis (eta ⁵ - propyl cyclopentadienyl) titanium diphenoxide, bis (eta ^{5-n-Buchirushikuro} pentadienyl) titanium diphenoxide, bis (eta ^5-n-butyl cyclopentadienyl) titanium di (4-hexyl-phenyl), bis (eta ⁵ - methylcyclopentadienyl) titanium difluoride, bis (eta ⁵ -1,3-Dimethylcyclopentadienyl) titanium difluoride Bis (eta ⁵ - ethyl cyclopentadienyl) titanium difluoride, bis (eta ⁵ - propyl cyclopentadienyl) titanium difluoride, bis (eta ^5-n-butyl cyclopentadienyl) titanium difluoride, Bis (η ⁵ -methylcyclopentadienyl) titanium dichloride,

Bis (η ⁵ -1,3-dimethylcyclopentadienyl) titanium dichloride, bis (η ⁵ -ethylcyclopentadienyl) titanium dichloride,
Bis (η ⁵ -propylcyclopentadienyl) titanium dichloride, bis (η ⁵ -n-butylcyclopentadienyl) titanium dichloride, bis (η ⁵ -methylcyclopentadienyl) titanium dibromide, bis (η ⁵ − 1,3-Dimethylcyclopentadienyl) titanium dibromide, bis (η ⁵ -ethylcyclopentadienyl) titanium dibromide, bis (η ⁵ -propylcyclopentadienyl) titanium dibromide, bis (η ⁵ -n -Butylcyclopentadienyl) titanium dibromide, bis (η ⁵ -methylcyclopentadienyl) titanium diiodide, bis (η ⁵ −
1,3-dimethylcyclopentadienyl) titanium diiodide, bis (η ⁵ -ethylcyclopentadienyl) titanium diiodide, bis (η ⁵ -propylcyclopentadienyl) titanium diiodide,

Bis (η ⁵ -n-butylcyclopentadienyl) titanium diiodide, bis (η ⁵ -methylcyclopentadienyl) titanium chloride methyl, bis (η ⁵ -di1,3-methylcyclopentadiene (Enyl) titanium chloride methyl, bis (η ⁵ -ethylcyclopentadienyl) titanium chloride methyl, bis (η ⁵ -propylcyclopentadienyl) titanium chloride methyl, bis (η ⁵ -n-butylcyclopentadienyl) titanium Chloride methyl, bis (η ⁵ −
Methylcyclopentadienyl) titanium dichloride ethoxide, bis (eta ^{5-1,3-dimethyl-cyclopentadienyl)} titanium chloride ethoxide, bis (eta ⁵ - ethyl cyclopentadienyl) titanium dichloride ethoxide, bis (eta ⁵ -propylcyclopentadienyl) titanium chloride ethoxide, bis (η ⁵ -n-butylcyclopentadienyl) titanium chloride ethoxide, bis (η ⁵ -methylcyclopentadienyl) titanium chloride phenoxide,
Bis (eta ^{5-1,3-dimethyl-cyclopentadienyl)}
Titanium chloride phenoxide, bis (η ⁵ -ethylcyclopentadienyl) titanium chloride phenoxide, bis (η ⁵ -propylcyclopentadienyl) titanium chloride phenoxide,

Bis (η ⁵ -n-butylcyclopentadienyl) titanium chloride phenoxide, bis (η
⁵ - cyclopentadienyl) titanium dibenzyl, bis (eta ^{5-1,3-dimethyl-cyclopentadienyl)} titanium dibenzyl, bis (eta ⁵ - ethyl cyclopentadienyl) titanium dibenzyl, bis (eta ⁵ −
Propyl cyclopentadienyl) titanium dibenzyl, bis (eta ^5-n-butyl cyclopentadienyl) titanium dibenzyl, bis (eta ⁵ - methyl cyclopentadienyl) titanium dicarbonyl, bis (eta ⁵ -1,
3-dimethylcyclopentadienyl) titanium dicarbonyl, bis (η ⁵ -ethylcyclopentadienyl) titanium dicarbonyl, bis (η ⁵ -propylcyclopentadienyl) titanium dicarbonyl, bis (η ⁵ −
Examples include n-butylcyclopentadienyl) titanium dicarbonyl.

These can be used alone or in combination with each other. These titanocene compounds having an alkyl group-substituted cyclopentadienyl group are not limited to the above examples, and those having a substitution number of the alkyl group of the cyclopentadienyl ring of 2, 3, or 4 are also suitably used. .

Each of these titanocene compounds hydrogenates the olefinically unsaturated double bond of the olefin compound at a high position and is also excellent in heat resistance. In particular, a conjugated diene polymer or a conjugated diene and a vinyl aromatic hydrocarbon is used. Desirable as a catalyst component (A) having a high hydrogenation activity for an olefinic unsaturated double bond in a copolymer with and a hydrogenated unsaturated double bond at a high position and selectively in a wide temperature range As bis (η ⁵ -methylcyclopentadienyl)
Titanium dichloride, bis (η ⁵ -ethylcyclopentadienyl) titanium dichloride, bis (η ⁵ −
Propylcyclopentadienyl) titanium dichloride, bis (η ⁵ -n-butylcyclopentadienyl) titanium dichloride, bis (η ⁵ -methylcyclopentadienyl) titanium dimethyl, bis (η ⁵ -ethylcyclopentadienyl) Titanium dimethyl, bis (η
⁵ -propylcyclopentadienyl) titanium dimethyl, bis (η ⁵ -n-butylcyclopentadienyl) titanium dimethyl,

Bis (η ⁵ -methylcyclopentadienyl) titanium di (p-tolyl), bis (η ⁵ -ethylcyclopentadienyl) titanium di (p-tolyl),
Bis (η ⁵ -propylcyclopentadienyl) titanium di (p-tolyl), bis (η ⁵ -n-butylcyclopentadienyl) titanium di (p-tolyl), bis (η
⁵ -methylcyclopentadienyl) titanium diphenyl, bis (η ⁵ -ethylcyclopentadienyl) titanium diphenyl, bis (η ⁵ -propylcyclopentadienyl) titanium diphenyl, bis (η ⁵ -n-butylcyclopentadiene Mention may be made of (enyl) titanium diphenyl.

Further, bis (η ⁵ -methylcyclopentadienyl) is particularly preferable because it can be stably handled even in air.
Titanium dichloride, bis (η ⁵ -n-butylcyclopentadienyl) titanium dichloride, bis (η
⁵ -methylcyclopentadienyl) titanium diphenyl, bis (η ⁵ -n-butylcyclopentadienyl) titanium diphenyl, bis (η ⁵ -methylcyclopentadienyl) titanium di (p-tolyl), bis (η ⁵ −
n-butylcyclopentadienyl) titanium di (p-
Trill).

On the other hand, as the catalyst component (B), among the known organometallic compounds / metal-containing compounds capable of reducing the alkyl group-substituted titanocene compound of the catalyst component (A), Li, Na, K and Mg are used. At least one reducing agent selected from compounds containing at least one of Zn, Al, Ca elements is used. These are organic lithium compounds, organic sodium compounds, organic potassium compounds,
Examples thereof include organic zinc compounds, organic magnesium compounds, organic aluminum compounds, organic calcium compounds, and the like, and the olefin compounds can be hydrogenated by using them alone or in combination with two or more kinds (A).

Specific examples of the Li-containing compound include methyllithium, ethyllithium, n-propyllithium, isopropyllithium, n-butyllithium, sec-butyllithium, isobutyllithium, t-butyllithium,
n-pentyl lithium, n-hexyl lithium, phenyl lithium, cyclopentadienyl lithium, m-tolyl lithium, p-tolyl lithium, xylyl lithium,
Dimethylaminolithium, diethylaminolithium, methoxylithium, ethoxylithium, n-propoxylithium, isopropoxylithium, n-butoxylithium, sec-butoxylithium, t-butoxylithium, pentyloxylithium, hexyloxylithium, heptyloxylithium, octyl. Examples include oxylithium, phenoxylithium, 4-methylphenoxylithium, benzyloxylithium, 4-methylbenzyloxylithium, and the like.

A lithium phenolate compound obtained by reacting a phenolic stabilizer with an alkyllithium is also used. Specific examples of such a phenol-based stabilizer include 1-oxy-3-methyl-4-isopropylbenzene, 2,6-di-t-butylphenol and 2,6-di-
t-butyl-4-ethylphenol, 2,6-di-t-
Butyl-p-cresol, 2,6-di-t-butyl-4
-N-butylphenol, 4-hydroxymethyl-2,
6-di-t-butylphenol, butylhydroxyanisole, 2- (1-methylcyclohexyl) -4,6-
Dimethylphenol, 2,4-dimethyl-6-t-butylphenol, 2-methyl-4,6-dinonylphenol
2,6-di-t-butyl-α-dimethylamino-p
-Cresol, methylene-bis- (dimethyl-4,6-)
Phenol), 2,2'-methylene-bis- (4-methyl-6-t-butylphenol), 2,2'-methylene-bis- (4-methyl-6-cyclohexylpheno-).
2,2'-methylene-bis- (4-ethyl-6-
t-butylphenol), 4,4'-methylene-bis-
(2,6-di-t-butylphenol), 2,2′-methylene-bis- (6-α-methyl-benzyl-p-cresol) and the like.

The most versatile 2,6-di-t-butyl-p
-6-Li-t in which the hydroxyl group of -cresol is -OLi
-Butyl-4-methylphenoxylithium is particularly preferably used. Further, an organosilicon lithium compound such as trimethylsilyllithium, diethylmethylsilyllithium, dimethylethylsilyllithium, triethylsilyllithium or triphenylsilyllithium may be used.

Specific examples of the Na-containing compound include methyl sodium, ethyl sodium, n-propyl sodium,
Isopropyl sodium, n-butyl sodium, se
c-butyl sodium, isobutyl sodium, t-butyl sodium, n-pentyl sodium, n-hexyl sodium, phenyl sodium, cyclopentadienyl sodium, m-tolyl sodium, p-tolyl sodium, xylyl sodium, sodium naphthalene, etc. Can be mentioned.

Specific examples of the K-containing compound include methyl potassium, ethyl potassium, n-propyl potassium, isopropyl potassium, n-butyl potassium, sec-butyl potassium, isobutyl potassium, t-butyl potassium and n.
-Pentyl potassium, n-hexyl potassium, triphenylmethyl potassium, phenyl potassium, phenylethyl potassium, cyclopentadienyl potassium, m-tolyl potassium, p-tolyl potassium, xylyl potassium,
Examples thereof include potassium naphthalene.

Some of the above organic alkali metal compounds and organic alkaline earth metal compounds are used as living anion polymerization initiators for conjugated diene compounds and / or vinyl aromatic hydrocarbon compounds. A conjugated diene-based polymer having a metal active end,
Alternatively, in the case of a copolymer of a conjugated diene and a vinyl aromatic hydrocarbon (living polymer), these active ends also act as the catalyst (B) component.

Examples of the Zn-containing compound include diethyl zinc, bis (η ⁵ -cyclopentadienyl) zinc, diphenyl zinc and the like. Further, examples of the Mg-containing compound include dimethyl magnesium, diethyl magnesium, dibutyl magnesium, ethyl butyl magnesium and methyl. Magnesium bromide, ethyl magnesium chloride, ethyl magnesium bromide, ethyl magnesium chloride, phenyl magnesium bromide, phenyl magnesium chloride, t-butyl magnesium chloride, t-butyl magnesium bromide and the like can be mentioned.

Further, as the Al-containing compound, trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, triphenyl aluminum, diethyl aluminum chloride, dimethyl aluminum chloride, ethyl aluminum dichloride, methyl aluminum sesquichloride, ethyl aluminum sesquichloride, diethyl aluminum hydride, Diisobutylaluminum hydride, triphenylaluminum, tri (2-ethylhexyl) aluminum, (2-ethylhexyl) aluminum dichloride, methylaluminoxane, ethylaluminoxane and the like can be mentioned.

In addition to these, alkali (earth) metal hydrides such as lithium hydride, potassium hydride, sodium hydride and calcium hydride,
2 such as sodium aluminum hydride, potassium aluminum hydride, diisobutyl sodium aluminum hydride, tri (t-butoxy) aluminum hydride, triethyl sodium aluminum hydride, diisobutyl sodium aluminum hydride, triethyl sodium aluminum hydride, triethoxy sodium aluminum hydride, triethyl lithium aluminum hydride A hydride containing at least one metal may be used. Further, a complex synthesized by previously reacting the organic alkali metal compound and the organic aluminum compound, a complex synthesized by previously reacting the organic alkali metal compound and the organic magnesium compound (art complex), and the like are also included. Be done.

The catalysts (A) and (B) components are essential,
The catalyst composition composed of both of these hydrogenates the unsaturated double bond of the olefin compound to a high position in a wide temperature range. (C) or (D) in addition to the components (A) and (B)
By combining the components, the storage stability of the catalyst is increased, the hydrogenation activity is reproducible, and it becomes easy to handle.

The catalyst (C) component is an olefinic unsaturated double bond-containing polymer having a ratio of 0.3 to 1 to the total amount of olefinic unsaturated double bonds in the side chain. Although it is a combination, an example of a monomer used for the production of this polymer is a conjugated diene, which is generally 4
˜Conjugated dienes having about 12 hydrocarbons. Specific examples include 1,3-butadiene, isoprene, 2,3-dimethylbutadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene, 4,5-diethyl- 1,3-octadiene, 3-butyl-1,3-octadiene and the like can be mentioned. These may be used alone or in combination of two or more. 1, which can be developed industrially and is relatively easy to handle
3-Butadiene and isoprene are particularly preferable, and polybutadiene, polyisoprene and butadiene / isoprene copolymer which are homopolymers or copolymers thereof are preferable. Further, norbornadiene, cyclopentadiene, 2,3-dihydrodicyclopentadiene and alkyl-substituted products thereof may be used alone or as a copolymer.

The catalyst component (C) polymer may have a number average molecular weight of 500 or more and 1,000,000 or less. When the number average molecular weight is less than 500, the effect of stabilizing the catalytic activity is reduced. A liquid rubber having a number average molecular weight of 500 or more that is easy to handle and has excellent solvent solubility is used. The liquid rubber is preferably liquid at normal temperature and has a number average molecular weight of 500 to 1
0000 is particularly good. Number average molecular weight is 10,000
When the above conditions are satisfied, there is no particular problem with the performance of the catalyst composition except that handling as a liquid becomes difficult.

The microstructure is most important in the polymer of the component (C). The "fraction of the olefinically unsaturated double bond of the side chain to the total olefinic unsaturated double bond" is defined as X, and the olefinically unsaturated carbon-carbon double bond in the side chain of the ((C) component polymer is shown. Number] = Y,
When [the total number of olefinic unsaturated carbon-carbon double bonds in the component (C) polymer] = Z, the value of X defined by X = Y / Z is preferably in the range of 0.3 to 1. Within this range, the terminal may have a functional group such as a hydroxyl group, a carboxyl group, an amino group and an epoxy group. This value range means that when polybutadiene is used as a specific example of the catalyst (C) component, all olefinically unsaturated double bonds (cis 1,4 bond, trans 1,4 bond, 1,
2 bonds) side chain olefinically unsaturated double bonds (1,
2 bonds) is preferably in the range of 0.3 to 1 (30 to 100%). If this ratio is less than 0.3, the hydrogenated catalyst composition after reduction becomes unstable and the storage stability deteriorates, which is not preferable.

Further, this polymer may be a copolymer with a conjugated diene / aromatic vinyl compound. Specific examples of the aromatic vinyl compound include styrene, t-butylstyrene, α-
Methylstyrene, p-methylstyrene, divinylbenzene, 1,1-diphenylethylene, N, N-diethyl-
Examples thereof include p-aminoethylstyrene, and styrene is particularly preferable. As a concrete example of the copolymer, a butadiene / styrene copolymer, an isoprene / styrene copolymer and the like are most suitable. These copolymers are random,
It may be a block, a star block, a tapered block, or the like, and is not particularly limited. The amount of the bound aromatic vinyl compound is preferably 70% or less. This amount is 70
%, The ratio of the olefinically unsaturated double bond in the side chain of the conjugated diene part to the total amount of the copolymer decreases, and the stabilizing effect of the catalyst decreases, resulting in a relatively large amount. Since the catalyst component (C) is required, the physical properties of the hydrogenated conjugated diene-based polymer and the copolymer of the conjugated diene and the vinyl aromatic hydrocarbon may change, so that it is substantially meaningless.

Most importantly, it is necessary that the ratio of the olefinically unsaturated double bond amount of the side chain of the conjugated diene part of the component (C) to the total olefinic double bond is 0.3 to 1. A more desirable fraction is 0.5 to 0.99. These catalyst components (C) may be polymerized by any known method such as radical polymerization, cationic polymerization, anionic polymerization and coordinated anionic polymerization, but the amount of olefinically unsaturated double bond in the side chain is increased. For this purpose, it can be obtained by living anionic polymerization using an organolithium or organosodium compound as a catalyst in a polar solvent or in the presence thereof, or by coordination anionic polymerization using a cobalt-based Ziegler-type catalyst, or ethylene and dicyclohexyl. It can be obtained by copolymerizing pentadienes.

Specific examples of the polar solvent include tetrahydrofuran, tetramethylethylenediamine, trimethylamine, triethylamine, ethyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether,
Examples include dipiperidinoethane. Methyllithium, ethyllithium, n-propyllithium, isopropyllithium, n-butyllium, sec as Li-based catalyst
-Butyl lithium, isobutyl lithium, tert-butyl lithium, n-pentyl lithium, n-hexyl lithium, trimethylsilyl lithium and the like can be mentioned. N
a-type catalyst as methyl sodium, ethyl sodium,
n-propyl sodium, isopropyl sodium, n
-Butyl sodium, sec-butyl sodium, isobutyl sodium, phenyl sodium, sodium naphthalene, cyclopentadienyl sodium and the like can be mentioned.

The catalyst (A), (B) and (C) or the catalyst composition comprising the components (A), (B) and (D) can be further improved in storage stability by using the catalyst (A ),
The combination with the components (B), (C) and (D) is most effective. The catalyst (D) component is an alcohol compound, an ether compound, a thioether compound, a ketone compound, a sulfoxide compound, a carboxylic acid compound, a carboxylic acid ester compound, an aldehyde compound, a lactam compound, a lactone compound, an amine compound, an amide. The compound is at least one polar compound selected from the group consisting of a compound, a nitrile compound, an epoxy compound, and an oxime compound. Specific examples of these polar compounds include the following compounds.

Of these, specific examples of the alcohol compound include methyl alcohol, ethyl alcohol, propyl alcohol, n-butyl alcohol, sec-butyl alcohol, isobutyl alcohol and tert-butyl alcohol. , N-amyl alcohol, isoamyl alcohol
, Hexyl alcohol and its isomers, heptyl alcohol and its isomers, octyl alcohol and its isomers, capryl alcohol, nonyl alcohol and its isomers, decyl alcohol and its isomers, Benzyl alcohol, phenol, cresol, 2,6-di-te
Monovalent alcohols such as rt-butyl-p-cresol, ethylene glycol, propylene glycol, butanediol, pentyl glycol, hexyl glycol, heptyl glycol and isomers thereof. Examples thereof include glycol (divalent alcohol) and the like. Further, it may be an alcohol compound having another functional group in one molecule, such as trivalent alcohol such as glycerin, ethanolamine, glycidyl alcohol or the like.

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

Specific examples of the thioether compound include dimethyl sulfide, diethyl sulfide and di-n.
-Butyl sulfide, di-sec-butyl sulfide,
Examples thereof include di-tert-butyl sulfide, diphenyl sulfide, methyl ethyl sulfide, ethyl butyl sulfide, thioanisole, ethyl phenyl sulfide, thiophene and tetrahydrothiophene.

Further, specific examples of the ketone compound include acetone, diethyl ketone, di-n-propyl ketone, diisopropyl ketone, di-n-butyl ketone and di-se.
Examples thereof include c-butyl ketone, di-tert-butyl ketone, benzophenone, methyl ethyl ketone, acetophenone, benzyl phenyl ketone, propiophenone, cyclopentanone, cyclohexanone, diacetyl, acetylacetone and benzoylacetone. Further, specific examples of the sulfoxide compound include dimethyl sulfoxide, diethyl sulfoxide, tetramethylene sulfoxide, pentamethylene sulfoxide, diphenyl sulfoxide, dibenzyl sulfoxide, p-tolyl sulfoxide and the like.

Further, specific examples of the carboxylic acid compound include formic acid, acetic acid, propionic acid, butyric acid, caproic acid, lauric acid, palmitic acid, stearic acid, cyclohexylpropionic acid, cyclohexylcaproic acid, benzoic acid, phenylacetic acid and o-toluyl. Acid, m-toluic acid, p-toluic acid, acrylic acid, methacrylic acid and other monobasic acids,
Dibasic acids such as oxalic acid, maleic acid, malonic acid, fumaric acid, succinic acid, adipic acid, pimelic acid, suberic acid, sebacic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, naphthalic acid, diphenic acid, etc. , Trimellitic acid
Pyromellitic acid and derivatives thereof can be mentioned. Further, it may be a compound having another functional group in one molecule, such as hydroxybenzoic acid.

Specific examples of the carboxylic acid ester include formic acid, acetic acid, propionic acid, butyric acid, caproic acid, lauric acid, palmitic acid, stearic acid, cyclohexylpropionic acid, cyclohexylcaproic acid, benzoic acid, phenylacetic acid, o- Toluic acid, m-toluic acid,
Monobasic acids such as p-toluic acid, acrylic acid, methacrylic acid, oxalic acid, maleic acid, malonic acid, fumaric acid, succinic acid, adipic acid, pimelic acid, suberic acid, sebacic acid, itaconic acid, phthalic acid, isophthalic acid Acid, dibasic acid such as terephthalic acid, naphthalic acid, diphenic acid, and methyl alcohol, ethyl alcohol, propyl alcohol, n
-Butyl alcohol, sec-butyl alcohol, isobutyl alcohol, tert-butyl alcohol, n-
Amyl alcohol, isoamyl alcohol, hexyl alcohol and its isomers, heptyl alcohol and its isomers, octyl alcohol and its isomers, capryl alcohol, nonyl alcohol and its isomers, decyl alcohol and its isomers, benzyl alcohol, phenol , Esters with alcohols such as cresol and glycidyl alcohol, and β-ketoesters such as methyl acetoacetate and ethyl acetoacetate.

Further, specific examples of the lactone compound include:
Examples include β-propiolactone, δ-valerolactone, ε-caprolactone and lactone compounds corresponding to the following acids. That is, as this acid, 2-methyl-3-hydroxypropionic acid, 3-hydroxynonane or 3
-Hydroxypelargonic acid, 2-dodecyl-3-hydroxypropionic acid, 2-cyclopentyl-3-hydroxypropionic acid, 2-n-butyl-3-cyclohexyl-3-hydroxypropionic acid, 2-phenyl-3-hydroxytridecane Acid, 2- (2-ethylcyclopentyl) -3-hydroxypropionic acid, 2-methylphenyl-3-hydroxypropionic acid, 3-benzyl-3-
Hydroxypropionic acid, 2,2-dimethyl-3-hydroxypropionic acid, 2-methyl-5-hydroxyvaleric acid, 3-cyclohexyl-5-hydroxyvaleric acid, 4-phenyl-5-hydroxyvaleric acid, 2 -Heptyl-4-cyclopentyl-5-hydroxypropylvaleric acid,

3- (2-cyclohexylethyl) -5-
Hydroxyvaleric acid, 2- (2-phenylethyl)-
4- (4-cyclohexylbenzyl) -5-hydroxyvaleric acid, benzyl-5-hydroxyvaleric acid, 3
-Ethyl-5-isopropyl-6-hydroxycaproic acid, 2-cyclopentyl-4-hexyl-6-hydroxycaproic acid, 2-cyclopentyl-4-hexyl-6
-Hydroxycaproic acid, 3-phenyl-6-hydroxycaproic acid, 3- (3,5-diethyl-cyclohexyl) -5-ethyl-6-hydroxycaproic acid, 4-
(3-Phenyl-propyl) -6-hydroxycaproic acid, 2-benzyl-5-ishibutyl-6-hydroxycaproic acid, 7-phenyl-6-hydroxyl-octenoic acid, 2,2-di (1-cyclohexenyl) -5-hydroxy-5-heptenoic acid, 2,2-dipropenyl-5-
Hydroxy-5-heptenoic acid, 2,2-dimethyl-4-
Propenyl-3-hydroxy-3,5-heptadienoic acid and the like can be mentioned.

Further, specific examples of the amine compound include methylamine, ethylamine, isopropylamine and n-
Butylamine, sec-butylamine, tert-butylamine, n-amylamine, sec-amylamine,
tert-amylamine, n-hexylamine, n-heptylamine, aniline, benzylamine, o-anisidine, m-anisidine, p-anisidine, α-naphthylamine, dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, Di-n-butylamine, di-sec-butylamine, diisobutylamine, di-tert-butylamine, di-n-amylamine, diisoamylamine, dibenzylamine, N-methylaniline, N-ethylaniline, N-ethyl-o. -Toluidine, N-ethyl-m-toluidine, N-ethyl-
p-toluidine,

Triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-amylamine, triisoamylamine, tri-n-hexylamine, tribenzylamine, triphenylmethylamine,
N, N-dimethylbenzylamine, N, N-dimethylaniline, N, N-diethylaniline, N, N-diethyl-o-toluidine, N, N-diethyl-m-toluidine, N, N-diethyl-p- Toluidine, N, N-dimethyl-α-naphthylamine, N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-tetraethylethylenediamine, pyrrolidine, piperidine,
Examples thereof include N-methylpyrrolidine, N-methylpiperidine, pyridine, piperazine, 2-acetylpyridine, N-benzylpiperazine, quinoline and morpholine.

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

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

Further, specific examples of the oxime compound include
Acetoxime, methyl ethyl ketone oxime, diethyl ketone oxime, acetophenone oxime, benzophenone oxime, benzyl phenyl ketone oxime, cyclopentanone oxime, cyclohexanone oxime,
Examples thereof include benzaldehyde oxime. The above polar compounds may be used alone or in combination of two or more.
Particularly preferred compounds that have a favorable effect on the hydrogenation activity are monohydric alcohol compounds, tertiary amine compounds, ether compounds, ketone compounds and carboxylic acid compounds.

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

The present invention can also be applied to selective hydrogenation of olefinically unsaturated double bonds of a conjugated diene copolymer or a copolymer of a conjugated diene and an olefin monomer. The selective hydrogenation here is to selectively hydrogenate the conjugated diene copolymer, the olefinically unsaturated double bond of the conjugated diene part of the copolymer of the conjugated diene and the olefin monomer, and the olefin. When a vinyl aromatic compound is used as a monomer,
The carbon-carbon double bond of the aromatic ring is meant to be substantially non-hydrogenated.

The selective hydrogenated product of the olefinically unsaturated double bond of the conjugated diene copolymer or the copolymer of the conjugated diene and the olefin monomer is industrially useful as an elastic body or a thermoplastic elastic body. .. The conjugated diene used for producing the conjugated diene polymer generally includes a conjugated diene having 4 to about 12 carbon atoms, and specific examples include 1,3-butadiene, isoprene, and 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. From the standpoint of obtaining an elastic body that can be industrially developed and has excellent physical properties,
1,3-butadiene and isoprene are preferred.

The microstructure of the butadiene portion includes 1,2
Although there are bonds and 1,4 bonds (cis + trans), both of the catalysts of the present invention can quantitatively hydrogenate.
Further, in the isoprene portion, there are olefinically unsaturated bonds in the side chains of 1,2 bonds, 3,4 bonds and the main chain of 1,4 bonds (cis + trans), and each has the following structure ( Chemical formula 9, Chemical formula 10, Chemical formula 11).

[0072]

[Chemical 9]

[0073]

[Chemical 10]

[0074]

[Chemical 11]

The structures and hydrogenation rates of these are ¹ H-NMR
Can be measured by Using the method of the present invention, the side chains of the 1,2 bond, 1,4 bond of the butadiene moiety and the 1,2 bond (Chemical formula 9), 3,4 bond (Chemical formula 10) of the isoprene moiety are selectively hydrogenated. It is possible to

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

To obtain the effect of the present invention of selectively hydrogenating only the unsaturated double bond of the conjugated diene unit and to obtain an industrially useful and valuable elastic body or thermoplastic elastic body, Copolymers of conjugated dienes and vinyl-substituted aromatic hydrocarbons are of particular interest. Specific examples of the vinyl aromatic hydrocarbon copolymerizable with at least one conjugated diene include styrene, tert-butylstyrene, α-methylstyrene, p-methylstyrene, divinylbenzene, and 1,1-.
Examples thereof include diphenylethylene, N, N-dimethyl-p-aminoethylstyrene, N, N-diethyl-p-aminoethylstyrene and the like, and styrene and / or α-methylstyrene are particularly preferable.

Specific examples of copolymers include butadiene / styrene copolymers, isoprene / styrene copolymers, butadiene / isoprene / styrene copolymers, etc., which give hydrogenated copolymers of high industrial value. Therefore, it is most suitable. These copolymers are not particularly limited and may be random, block or tapered block copolymers. Under the catalyst composition of the present invention and preferred hydrogenation conditions, hydrogenation of carbon-carbon double bonds (aromatic rings) of vinyl-substituted aromatic hydrocarbon units in such copolymers does not substantially occur.

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

In the hydrogenation reaction of the present invention, generally, the solution to be hydrogenated is maintained at a predetermined temperature in hydrogen or an inert atmosphere, and a hydrogenation catalyst is added with or without stirring, Then, hydrogen gas is introduced and pressurized to a predetermined pressure. An inert atmosphere is, for example, nitrogen, helium,
It means an atmosphere that does not react with any participant in the hydrogenation reaction such as neon or argon. Air and oxygen are not preferable because they oxidize the catalyst components and deactivate the catalyst.

The hydrogenation catalyst composition of the present invention comprises (A),
The order of adding the components (B), (C) and (D) may be arbitrary and is not particularly limited. Therefore, the catalyst composition of the present invention may be prepared in a catalyst tank separately from the reaction system and then introduced into the reaction system, or each catalyst component may be introduced into the reaction system separately. When a hydrogenated conjugated diene polymer or a copolymer of a conjugated diene and a vinyl aromatic hydrocarbon is obtained by living anionic polymerization using an organic alkali metal or an organic alkaline earth metal as an initiator,
As will be described later, the reduction ratio between the catalyst (A) component and the component (B) is important.
Part or all can be used as an ingredient.

In order to adjust this ratio, it is necessary to inactivate part or all of the active terminals, but usually, a molar equivalent to the active terminals or an excess of the inactivating agent is added. An excess alcohol or ketone compound is preferably used as the deactivator. However, when these deactivators are present in the reaction system, they also act as catalyst (D) component or a part of (D) component. I reckon. Of course, regardless of the reaction system and the catalyst system, (A) (B),
(A) (B) (C), (A) (B) (D) and (A)
If it is composed of the components (B), (C) and (D), it is included in the scope of the present invention.

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

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

When the catalyst composition is prepared in advance in the catalyst tank, it is necessary to transfer the prepared hydrogenation catalyst composition to the hydrogenation reactor (hydrogenation tank). In this case, it is carried out under hydrogen atmosphere. Is most desirable. The temperature when transferring is -30 ° C.
It is preferable to add at a temperature of from 1 to 100 ° C., preferably from −10 to 50 ° C. immediately before the hydrogenation reaction. The mixing ratio of each catalyst component for exhibiting high hydrogenation activity and hydrogenation selectivity is the ratio of the number of moles of metal of the catalyst component (B) to the number of moles of the catalyst component (A) (hereinafter Metal (B)). / Me
It is in the range of about 20 or less in terms of tal (A) molar ratio.

Even if Metal (B) / Metal (A) molar ratio = 0, that is, even if Metal (B) does not exist, quantitative hydrogenation can be carried out by thermal reduction, but at a higher temperature for a longer time. However, a high catalyst amount is required, which is not preferable. If the molar ratio of Metal (B) / Metal (A) exceeds 20, not only is it uneconomical to use an excessive amount of expensive catalyst component (B) that does not contribute to substantial activity improvement, but also unnecessary side reactions. Is likely to be caused and is not preferable. Metal (B) / Metal (A) molar ratio = 0.
The range of 5 to 10 is most suitable for remarkably improving the hydrogenation activity.

When the substance to be hydrogenated is a living polymer obtained by living anionic polymerization, the living end acts as a reducing agent. In order to achieve the (B) / Metal (A) molar ratio, it is preferable to deactivate the compound with various active hydrogen or halogen.

Water and methanol, ethanol, n-propanol, and n-as the compound having active hydrogen.
Butanol, sec-butanol, t-butanol, 1
-Pentanol, 2-pentanol, 3-pentanol, 1-hexanol, 2-hexanol, 3-hexanol, 1-heptanol, 2-heptanol, 3-heptanol, 4-heptanol, octanol, nonanol, decanol, undecanol, Alcohols such as lauryl alcohol, allyl alcohol, cyclohexanol, cyclopentanol, and benzyl alcohol, phenol, o-cresol, m-cresol, p-cresol, p-allylphenol, 2,6-di-t-butyl-p. -Phenols such as cresol, xylenol, dihydroanthraquinone, dihydroxycoumarin, 1-hydroxyanthraquinone, m-hydroxybenzyl alcohol, resorcinol and leucoaurine.

As the acid, acetic acid, propionic acid, butyric acid,
Examples thereof include organic carboxylic acids such as isoacetic acid, pentanoic acid, hexanoic acid, heptanoic acid, decalic acid, myristic acid, stearic acid, behenic acid, and benzoic acid.
As halogen-containing compounds, benzyl chloride, trimethylsilyl chloride (bromide), t-butylsilyl chloride (bromide), methyl chloride (bromide), ethyl chloride (bromide), propyl chloride (bromide), n-butyl chloride (bromide), etc. Can be mentioned. These may be used alone or in combination of two or more.

The catalyst (C) component is preferably added in an amount of 10 to 500 by weight with respect to the catalyst of the catalyst (A) component. 1
If it is less than 0, the effect of stabilizing the storage and reducing the amount of the catalyst becomes small. Even if this ratio exceeds 500, the hydrogenation activity is good, but when the substance to be hydrogenated is a polymer, it is difficult to separate the hydrogenated polymer and the catalyst component (C), so that the physical properties, etc. May affect the.

When the catalyst composition of the present invention is prepared separately from the reaction system, the product to be hydrogenated is an olefinically unsaturated double bond-containing polymer, and the side chain contains an olefinically unsaturated double bond-containing polymer. The amount is 0,0 to the total olefinically unsaturated double bond.
In the case of 3 to 1, this may be used as the catalyst component (C) or may be used as a mixture with another catalyst (C) component.

The catalyst component (D) is added in a molar ratio of (D) / (B) to 0.0 with respect to the catalyst of the catalyst component (B).
High hydrogenation activity in the range of 1 to 10 and storage stability
The hydrogenation activity persistence becomes extremely high.

The amount of catalyst added was 0.10 per 100 g of the product to be hydrogenated.
001 to 20 mmol is sufficient. Within this addition amount range, it is possible to preferentially hydrogenate the olefinically unsaturated double bond of the hydrogenated substance, and the hydrogenation of the double bond of the aromatic ring in the copolymer does not substantially occur. As a result, extremely high hydrogenation selectivity is realized. The hydrogenation reaction is possible even if the amount of addition exceeds 20 millimoles, but use of an excessive amount of catalyst becomes uneconomical and disadvantageous in that catalyst deashing and removal after the hydrogenation reaction become complicated. Further, the preferable amount of the catalyst to quantitatively hydrogenate the unsaturated double bond of the conjugated diene unit of the polymer under the selected conditions is 0.01 to 5 mmol per 100 g of the polymer.

The hydrogenation reaction of the present invention is carried out using molecular hydrogen, and more preferably, it is introduced in the form of gas into the substance to be hydrogenated. The hydrogenation reaction is more preferably carried out under stirring,
The introduced hydrogen can be brought into contact with the substance to be hydrogenated sufficiently quickly. The hydrogenation reaction is generally carried out in the temperature range of 0 to 200 ° C. If the temperature is lower than 0 ° C, the hydrogenation rate becomes slow and a large amount of catalyst is required, which is not economical, and if the temperature exceeds 200 ° C, side reactions, decomposition and gelation are likely to occur simultaneously.
Since the catalyst is also deactivated, the hydrogenation activity is reduced, which is not preferable. A more desirable temperature range is 20 to 180 ° C.

The pressure of hydrogen used in the hydrogenation reaction is preferably 1 to 100 kg / cm ² . Since a substantially plateau becomes slower water添速degree is less than 1 kg / cm ² can become difficult to raise the degree of hydrogenation, the pressure exceeding 100 kg / cm ² hydrogenation reaction is substantially complete at the same time as the step-up, substantially It is meaningless and causes unwanted side reactions and gelation, which is not preferable. More preferable hydrogenated hydrogen pressure is 2 to 30 k
Although it is g / cm ² , the optimum hydrogen pressure is selected in consideration of the amount of catalyst added and the like, and it is preferable that the hydrogen pressure is selected on the high pressure side in practice as the amount of the suitable catalyst decreases. .. The hydrogenation reaction time of the present invention is usually several seconds to 50 hours. The hydrogenation reaction time and hydrogenation pressure are appropriately selected within the above range depending on the desired hydrogenation rate.

According to the method of the present invention, the olefinic unsaturated double bond of the olefin compound, the conjugated diene copolymer and the olefinically unsaturated double bond in the copolymer of the conjugated diene and the vinyl aromatic hydrocarbon are Any hydrogenation rate can be obtained according to the purpose. A hydrogenation rate of 95% or more is sufficiently possible.

The hydrogenated target product can be easily separated from the solution subjected to the hydrogenation reaction using the catalyst of the present invention by chemical or physical means such as distillation or precipitation. In particular,
When the substance to be hydrogenated is a polymer, the catalyst solution is removed from the polymer solution subjected to the hydrogenation reaction by the method of the present invention, if necessary, and the hydrogenated polymer is separated from the solution. be able to. As a method of separation, for example, a method of adding a polar solvent which is a poor solvent for the hydrogenated polymer such as acetone or alcohol to the reaction solution after hydrogenation to precipitate and recover the polymer, and stirring the reaction solution in hot water Examples of the method include a method of distilling and recovering the solvent together with the solvent after charging, or a method of directly heating the reaction solution to distill off the solvent.

The hydrogenation method of the present invention is characterized in that the amount of the hydrogenation catalyst used is smaller. Therefore, when the olefin compound is a polymer, even if the hydrogenated catalyst remains in the polymer as it is, it does not significantly affect the physical properties of the obtained hydrogenated polymer, and in the isolation process of the hydrogenated polymer, the amount of the catalyst is large. Since a part is decomposed, removed and removed from the polymer, no special operation for deashing or removing the catalyst is required and it can be carried out by an extremely simple process. Secondly, the catalyst is excellent in heat resistance, and the hydrogenation rate does not easily decrease even if the temperature is relatively low, so that it shows high activity in the hydrogenation reaction of an olefin compound in a wide temperature range. Thirdly, the storage stability and activity stability are extremely excellent. Therefore, the activity of the catalyst almost continues to the initial hydrogenation activity even after several months.

[0099]

The present invention will be described in detail with reference to the following examples, but the present invention is not limited thereto. The hydrogenation catalysts used in Examples and Comparative Examples are shown below.

[Catalyst (A) component] (1) Bis (η ⁵ -methylcyclopentadienyl) titanium dichloride; used was a reagent manufactured by Nippon Fine Chemical Co., Ltd., which was recrystallized in dichloromethane. (2) Bis (η ⁵ -n-butylcyclopentadienyl) titanium dichloride; similar to (1). Similar to (1), (3) bis (eta ^{5-1,3-dimethyl-cyclopentadienyl)} titanium dichloride. (4) Bis (η ⁵ -methylcyclopentadienyl) di-p
-Trirutitanium; synthetic product was recrystallized in dichloromethane before use. (5) Bis (η ⁵ -methylcyclopentadienyl) di-m
-Tolyltitanium; synthetic product was recrystallized and used.

(6) Bis (η ⁵ -1,3-dimethylcyclopentadienyl) di-p-tolyltitanium; The synthetic product was recrystallized in dichloromethane and used. (7) Bis (η ⁵ -1,3-dimethylcyclopentadienyl) di-m-tolyltitanium; the synthetic product was recrystallized in dichloromethane and used. (8) Bis (η ⁵ -1,3-dimethylcyclopentadienyl) di-3,4-xylyl titanium; The synthetic product was recrystallized and used. (9) Bis (η ⁵ -n-butylcyclopentadienyl) di-p-tolyltitanium; similar to (4). (10) Bis (η ⁵ -n-butylcyclopentadienyl)
Di-m-tolyl titanium: similar to (4). (11) Bis (η ⁵ -cyclopentadienyl) titanium dichloride; Kanto Kagaku Co., Ltd. reagent first-grade reagent recrystallized in dichloromethane was used. (12) Bis (η ⁵ -pentamethylcyclopentadienyl) titanium dichloride; Aldrich reagent was used as it was without purification.

[Catalyst (B) component] (1) sec-Butyllithium: A hexane solution (reagent manufactured by Kanto Kagaku) was filtered off under an inert atmosphere, and a yellow transparent portion was used. (2) Ethyl butyl magnesium: A pentane solution (reagent manufactured by Kanto Kagaku) was used as it was. (3) Triisobutylaluminum: A hexane solution (manufactured by Tosoh Akzo) was used as it was. (4) Triethylaluminum; hexane solution (Tosoh
Akzo) was used as it was.

[Catalyst (D) component] (1) Methanol; a reagent manufactured by Wako Pure Chemical Industries, Ltd. under reflux dehydration in the presence of metallic Mg was used. (2) t-Butanol: Wako Pure Chemical Industries, Ltd. reagents dehydrated with molecular sieves were used. (3) Ethylene glycol; CaH ₂ reagent from Wako Pure Chemical Industries
What was reflux dehydrated in the presence was used. (4) Tetrahydrofuran: a reagent manufactured by Kanto Kagaku Co., Ltd. was used after reflux dehydration in the presence of benzophenone ketyl. (5) Acetone: A reagent manufactured by Wako Pure Chemical Industries, Ltd. was used after reflux dehydration in the presence of CaH ₂ .

(6) Ethyl acetate; Caged reagent manufactured by Wako Pure Chemical Industries, Ltd.
The one dehydrated under reflux in the presence of H ₂ was used. (7) ε-caprolactone; a reagent manufactured by Wako Pure Chemical Industries, Ltd. is CaH ₂
What was reflux dehydrated in the presence was used. (8) Triethylamine: A reagent manufactured by Wako Pure Chemical Industries, Ltd. was used after reflux dehydration in the presence of Na. (9) N, N, N ′, N′-tetramethylethylenediamine; a reagent manufactured by Wako Pure Chemical Industries, Ltd. was used after reflux dehydration in the presence of Na. The hydrogenation rate was determined by ¹ H-NMR, and the decrease in the signal intensity of olefinic hydrogen before and after the reaction was determined using the signal intensity of hydrogen in the aromatic ring of the styrene block portion as an internal standard.

Example 1 A sufficiently dried 500 ml three-necked flask was charged with bis (η
0.0181 mol of ⁵ -methylcyclopentadienyl) titanium dichloride and 200 ml of dehydrated ether were placed in the flask. Next, 0.037 mol of p-tolyllithium and 100 m of diethyl ether were placed in an equal pressure dropping funnel.
1 was added. The flask was cooled to -20 ° C, and the ether solution of p-tolyllithium in the isobaric dropping funnel was slowly added dropwise over 20 minutes while vigorously stirring the inside of the flask with a magnetic stirrer. After dropping, the mixture was stirred for 20 minutes, and then 5 ml of methylene chloride was added to decompose excess p-tolyllithium, and the mixture was slowly returned to room temperature. By-produced LiCl was filtered off and the ether was distilled off, and then 200 ml of dehydrated methylene chloride was added. After filtering off the insoluble matter,
The methylene chloride was distilled off and then dried under reduced pressure. Screw (η ⁵
4.7 g of -methylcyclopentadienyl) di-p-tolyltitanium were obtained. Yield 68%, product is ¹ H-NM
From the R and MS spectra, it was confirmed to be the desired product.
The ¹ H-NMR chart of the product is shown in FIG. 1, and the results in which the signals a to e are assigned are shown in Chemical formula 12. The MS spectrum of the product is shown in FIG.

[0106]

[Chemical 12]

Example 2 A well-dried 500 ml three-necked flask was charged with bis (η
0.0181 mol of ⁵ -methylcyclopentadienyl) titanium dichloride and 200 ml of dehydrated ether were placed in the flask. Next, 0.037 mol of m-tolyllithium and 100 m of diethyl ether were placed in an equal pressure dropping funnel.
1 was added. The flask was cooled to −20 ° C., and the ether solution of m-tolyllithium in the isobaric dropping funnel was slowly added dropwise over 20 minutes while vigorously stirring the inside of the flask with a magnetic stirrer. After dropping, the mixture was stirred for 20 minutes, and then 5 ml of methylene chloride was added to decompose excess m-tolyllithium, and the mixture was slowly returned to room temperature. By-produced LiCl was filtered off and the ether was distilled off, and then 200 ml of dehydrated methylene chloride was added. After filtering off the insoluble matter,
The methylene chloride was distilled off and then dried under reduced pressure. Screw (η ⁵
4.5 g of -methylcyclopentadienyl) di-m-tolyltitanium was obtained. Yield 64%. The product is ¹ H-NM
From the R and MS spectra, it was confirmed to be the desired product.

Example 3 A sufficiently dried 500 ml three-necked flask was charged with bis (η
0.0139 mol of ^5- n-butylcyclopentadienyl) titanium dichloride and 200 ml of dehydrated ether were placed in the flask. Next, 0.0277 mol of an ether solution of p-tolyllithium and 100 ml of diethyl ether were placed in an equal pressure dropping funnel. Flask at -20 ° C
The mixture was cooled to 0.degree. C., and the ether solution of p-tolyllithium in the isobaric dropping funnel was slowly added dropwise over 20 minutes while vigorously stirring the inside of the flask with a magnetic stirrer. After dropping, the mixture was stirred for 20 minutes, and then 5 ml of methylene chloride was added to decompose excess p-tolyllithium, and the mixture was slowly returned to room temperature. By-produced LiCl was filtered off. After the ether was distilled off, 200 ml of dehydrated methylene chloride was added. The insoluble matter was filtered off, methylene chloride was distilled off, and the residue was dried under reduced pressure. 4 g of bis (η ⁵ -n-butylcyclopentadienyl) di-p-tolyltitanium was obtained. The yield was 61%, and the product was confirmed to be the target product from ¹ H-NMR and MS spectra. The ¹ H-NMR chart of the product is shown in FIG. 3, and the results in which the signals a to f are assigned are shown in Chemical formula 13. The MS spectrum of the product is shown in FIG.

[0109]

[Chemical 13]

Example 4 A well-dried 500 ml three-necked flask was charged with bis (η
0.0139 mol of ^5- n-butylcyclopentadienyl) titanium dichloride and 200 ml of dehydrated ether were placed in the flask. Next, 0.0277 mol of m-tolyllithium and diethyl ether 1 were placed in an equal pressure dropping funnel.
00 ml was added. The flask was cooled to −20 ° C., and the ether solution of m-tolyllithium in the isobaric dropping funnel was slowly added dropwise over 20 minutes while vigorously stirring the inside of the flask with a magnetic stirrer. After dropping, the mixture was stirred for 20 minutes, and then 5 ml of methylene chloride was added to decompose excess m-tolyllithium, and the mixture was slowly returned to room temperature. By-produced LiCl was filtered off. After the ether was distilled off, 200 ml of dehydrated methylene chloride was added. The insoluble matter was filtered off, methylene chloride was distilled off, and the residue was dried under reduced pressure. 4.1 g of bis (η ⁵ -n-butylcyclopentadienyl) di-m-tolyltitanium was obtained. Yield 63%.
The product was confirmed to be the desired product by ¹ H-NMR and MS spectrum.

Example 5 A sufficiently dried 500 ml three-necked flask was charged with bis (η
⁵ -1,3-dimethyl-cyclopentadienyl) titanium dichloride 0.0164mol with dry ether 200
ml was placed in the flask. Next, 0.0328 mol of p-tolyllithium and 100 ml of diethyl ether were placed in an equal pressure dropping funnel. The flask was cooled to −20 ° C., and the ether solution of m-tolyllithium in the isobaric dropping funnel was slowly added dropwise over 20 minutes while vigorously stirring the inside of the flask with a magnetic stirrer. 20 after dropping
After stirring for a minute, 5 ml of methylene chloride was added to decompose excess p-tolyllithium, and the temperature was slowly returned to room temperature. By-produced LiCl was filtered off. After the ether was distilled off, 200 ml of dehydrated methylene chloride was added. The insoluble matter was filtered off, methylene chloride was distilled off, and the residue was dried under reduced pressure. Bis (eta ^{5-1,3-dimethyl-cyclopentadienyl)} di -m- tolyl titanium to give 4.3 g. The product was confirmed to be the desired product by ¹ H-NMR and MS spectrum.

Example 6 A sufficiently dried 500 ml three-necked flask was charged with bis (η
⁵ -1,3-dimethyl-cyclopentadienyl) titanium dichloride 0.0164mol with dry ether 200
ml was placed in the flask. Next, 0.0328 mol of 3,4-xylyllithium and 100 ml of diethyl ether were placed in an equal pressure dropping funnel. The flask was cooled to −20 ° C., and the ether solution of 3,4-xylyllithium in the isobaric dropping funnel was slowly added dropwise over 20 minutes while vigorously stirring the inside of the flask with a magnetic stirrer.
After the dropwise addition, the mixture was stirred for 20 minutes, then 5 ml of methylene chloride was added to decompose excess 3,4-xylyllithium, and the temperature was slowly returned to room temperature. By-produced LiCl was filtered off. After distilling off the ether, dehydrated methylene chloride 200
ml was added. The insoluble matter was filtered off, methylene chloride was distilled off, and the residue was dried under reduced pressure. 3.5 g of bis (η ⁵ -1,3-dimethylcyclopentadienyl) di-3,4-xylyl titanium was obtained. The product was confirmed to be the desired product by ¹ H-NMR and MS spectrum.

Example 7 Asahi Kasei Tuffprene A (styrene /
Butadiene-based block copolymer) was dissolved in 5 g of cyclohexane and 30 g of cyclohexane to completely replace hydrogen. At room temperature, 0.074 mmol of bis (η ⁵ -methylcyclopentadienyl) titanium dichloride was added as the catalyst (A) component (700 ppm as Ti to the polymer), and then sec-butyl lithium was added as the catalyst (B) component. 0.
222 mmol was added. The hydrogen pressure was increased to 10 kg / cm ² G, the mixture was stirred at 100 ° C. for 30 minutes, and a hydrogenation reaction was performed.
The obtained hydrogenated polymer solution was precipitated in a large amount of methanol to recover the hydrogenated polymer, which was then extracted with acetone and dried in vacuum, and ¹ H-NMR measurement was performed. The fact that the hydrogenated carbon-carbon double bond is only in the polybutadiene part and that the main chain is not cleaved
Confirmed by C. The results are shown in Table 1.

Example 8 The same procedure as in Example 7 was carried out except that ethylbutylmagnesium was used as the catalyst (B) component. The results are shown in Table 1. Example 9 The procedure of Example 7 was repeated except that triethylaluminum was used as the catalyst (B) component. The results are shown in Table 1. Example 10 The procedure of Example 7 was repeated except that bis (η ⁵ -n-butylcyclopentadienyl) titanium dichloride was used as the catalyst (A) component. The results are shown in Table 1. Example 11 In Example 7, bis (η ⁵ -1,3-) was used as the catalyst (A) component.
Dimethylcyclopentadienyl) titanium dichloride was used, except that the same procedure was performed. The results are shown in Table 1.

Example 12 The same procedure as in Example 7 was repeated except that bis (η ⁵ -n-butylcyclopentadienyl) titanium dichloride was used as the component (A) and ethylbutylmagnesium was used as the component (B). It was The results are shown in Table 1. Example 13 Ethyl butyl magnesium 0.1 as the component of the catalyst (B)
48 mmol, triisobutylaluminum 0.074
Example 10 except that the complex synthesized from mmol was used.
And went exactly the same. The results are shown in Table 1. Example 14 In Example 7, bis (η ⁵ -1,3-) was used as the catalyst (A) component.
Except that dimethylcyclopentadienyl) titanium dichloride and ethylbutylmagnesium were used as the catalyst (B) component, the same procedure was carried out. The results are shown in Table 1. Example 15 Ethyl butyl magnesium 0.1 as a catalyst (B) component
48 mmol, triisobutylaluminum 0.074
Example 14 except that the complex synthesized from mmol was used.
And went exactly the same. The results are shown in Table 1.

Example 16 The same procedure as in Example 7 was carried out except that triethylaluminum was used as the catalyst (B) component. The results are shown in Table 1. Example 17 The procedure of Example 7 was repeated except that bis (η ⁵ -n-butylcyclopentadienyl) titanium dichloride was used as the catalyst (A) component and triethylaluminum was used as the catalyst (B) component. The results are shown in Table 1. Example 18 In Example 7, bis (η ⁵ -1,3-) was used as the catalyst (A) component.
The procedure was exactly the same except that dimethylcyclopentadienyl) titanium dichloride was used and triethylaluminum was used as the catalyst (B) component. The results are shown in Table 1. Example 19 Bis (η ⁵ -methylcyclopentadienyl) di-p-tolyl titanium was used as the component (A) in Example 7,
Sec-butyllithium 0.074 m as component (B)
The procedure was exactly the same except that mol was used. The results are shown in Table 1.

Example 20 Bis (η ⁵ -n-butylcyclopentadienyl) di-p-tolyltitanium as the catalyst (A) component in Example 7,
Sec-butyllithium 0.074 m as component (B)
The procedure was exactly the same except that mol was used. The results are shown in Table 1. Example 21 Bis (η ⁵ -n-butylcyclopentadienyl) di-m-tolyl titanium was used as the component (A) in Example 7,
Sec-butyllithium 0.074 m as component (B)
The procedure was exactly the same except that mol was used. The results are shown in Table 1. Example 22 In Example 7, bis (η ⁵ -1,3-) was used as the catalyst (A) component.
Dimethylcyclopentadienyl) di-p-tolyltitanium, sec-butyllithium as component (B) 0.0
The procedure was exactly the same except that 74 mmol was used. The results are shown in Table 1. Example 23 In Example 7, bis (η ⁵ -1,3-) was used as the catalyst (A) component.
Except that dimethylcyclopentadienyl) di-3,4-xylyl titanium and 0.074 mmol of sec-butyllithium as the component (B) were used, the same procedure was carried out.
The results are shown in Table 1.

Example 24 20 ml of dried cyclohexane was added to a 200 ml pressure-resistant glass bottle substituted with argon, and then 0.148 mmol of bis (η ⁵ -methylcyclopentadienyl) titanium dichloride as a component of catalyst (A) and catalyst ( 1.5 g of liquid 1,2-polybutadiene (Nisso B-1000: 1,2-vinyl bond amount 85%) manufactured by Nippon Soda Co., Ltd. was added as component C), and sec-butyllithium was then added as the component (C) of catalyst. 0.4 at room temperature with stirring
44 mmol was added. After stirring for 5 minutes, 0.450 mmo of t-butyl alcohol was used as the catalyst component (D).
1 was added. Using 1/2 volume of this catalyst composition solution as a catalyst, hydrogenation reaction was carried out under exactly the same conditions as in the other examples. Table 2 shows the results. Example 25 The remaining catalyst composition solution obtained in Example 24 was stored in a refrigerator (10 ° C.) for 2 months. Using the whole amount of this as a catalyst, hydrogenation reaction was carried out under exactly the same conditions as in the other examples.
Table 2 shows the results.

Example 26 The same procedure as in Example 7 was carried out except that the addition amount of the catalysts (A) and (B) was scaled to 1/5. Table 2 shows the results. Example 27 The procedure of Example 26 was repeated, except that the hydrogenation temperature was changed to 60 ° C. Table 2 shows the results. Example 28 The procedure of Example 24 was repeated, except that methanol was used as the catalyst (D) component. Table 2 shows the results. Example 29 The procedure of Example 24 was repeated, except that 0.225 mmol of ethylene glycol was used as the catalyst (D) component. Table 2 shows the results. Example 30 The procedure of Example 24 was repeated, except that tetrahydrofuran was used as the catalyst (D) component. Table 2 shows the results.

Example 31 The same procedure as in Example 24 was repeated except that acetone was used as the catalyst (D) component. Table 2 shows the results. Example 32 The procedure of Example 24 was repeated, except that ethyl acetate was used as the catalyst (D) component. Table 2 shows the results. Example 33 The same procedure as in Example 24 was carried out except that ε-caprolactone was used as the catalyst (D) component. Table 2 shows the results. Example 34 The procedure of Example 24 was repeated, except that triethylamine was used as the catalyst (D) component. Table 2 shows the results. Example 35 N, N, N ′, N ′ as the catalyst (D) component in Example 24
-Exactly the same except that tetramethylethylenediamine was used. Table 2 shows the results.

Comparative Example 1 The same conditions as in Example 26 were used except that bis (η ⁵ -cyclopentadienyl) titanium dichloride was used as the catalyst (A) component. Table 2 shows the results. Comparative Example 2 The same conditions as in Example 26 were used except that bis (η ⁵ -pentamethylcyclopentadienyl) titanium dichloride was used as the catalyst (A) component. Table 2 shows the results.

Comparative Example 3 In exactly the same manner as in Example 7, the polymer, the catalysts (A) and (B) components were put in 250 ml autoclave and stored in a refrigerator for 2 months without applying hydrogen pressure. . After that, increase the hydrogen pressure to 1
A hydrogenation reaction was carried out at 100 ° C. for 30 minutes by applying 0 kg / cm ² G. Table 2 shows the results. Comparative Example 4 The same procedure as in Example 27 was repeated except that bis (η ⁵ -pentamethylcyclopentadienyl) titanium dichloride was used as the catalyst (A) component. Table 2 shows the results.

[0123]

[Table 1]

[0124]

[Table 2]

[0125]

[Table 3]

[0126]

[Table 4]

[0127]

As described above, by adopting the catalyst composition of the present invention and the hydrogenation method using the catalyst composition, the olefin compound / conjugated diene polymer or the weight of the conjugated diene and the vinyl aromatic hydrocarbon can be reduced. It has become possible to hydrogenate the olefinically unsaturated double bond of the conjugated diene part of the coalescence to a highly selective high position in a wide temperature range. Also,
The storage stability of the catalyst is also dramatically improved, and it can be handled stably without being affected by the preparation state of the catalyst or impurities in the system.
Especially as a result of improved heat resistance, it became possible to set the hydrogenation temperature higher than that of conventional titanocene-based catalysts, resulting in an increase in reaction rate and a decrease in polymer solution viscosity. Is significantly shortened and productivity is significantly improved. Further, the method of the present invention can be applied not only to a batch hydrogenation process but also to a continuous hydrogenation process. The hydrogenated polymer obtained by the method of the present invention is used as an elastic body excellent in weather resistance and oxidation resistance, a thermoplastic elastic body or a thermoplastic resin, and an additive such as an ultraviolet absorber, oil or filler. Is used and is used by blending with other elastic bodies and resins, and is extremely useful industrially.

[Brief description of drawings]

FIG. 1 ¹ H—N of bis (η ⁵ -methylcyclopentadienyl) di-p-tolyl titanium obtained in Example 1.
It is an MR spectrum figure.

FIG. 2 is a bis (η ⁵ -methylcyclopentadienyl) di-p-tolyltitanium MS spectrum diagram obtained in Example 1.

FIG. 3 ¹ H of bis (η ⁵ -n-butylcyclopentadienyl) di-p-tolyl titanium obtained in Example 3
-NMR spectrum diagram.

4 is a bis (η ⁵ -n-butylcyclopentadienyl) di-p-tolyltitanium MS spectrum diagram obtained in Example 3. FIG.

Claims (6)

[Claims] 1. A titanocene compound represented by the following general formula (Formula 1): (However, R ¹ and R ² represent a group selected from hydrogen and a C _{1 to} C ₁₂ hydrocarbon group, and R ¹ and R ² may be the same or different. However, R ¹ and R ² Are all hydrogen or all C _{1 to} C ₁₂ hydrocarbon groups R ³ , R ⁴
Represents hydrogen or a group selected from C _{1 to} C ₄ hydrocarbon groups, and R ³ and R ⁴ may be the same or different. (Except when R ³ and R ⁴ are all hydrocarbon groups) 2. A catalyst composition for hydrogenating an olefin compound, wherein the catalyst composition comprises the following components (A) and (B). (A) At least one titanocene compound represented by the following general formula (Formula 2): (However, R ⁵ and R ⁶ represent a group selected from hydrogen, a C _{1 to} C ₁₂ hydrocarbon group, an aryloxy group, an alkoxy group, a halogen group and a carbonyl group, and R ⁵ and R ⁶ are the same. Or R ¹ and R ² are hydrogen and C _1-
Represents a group selected from C ₁₂ hydrocarbon groups, R ¹ , R ²
May be the same or different. Provided that R ¹ and R ² are all hydrogen or all are C _{1 to} C ₁₂ hydrocarbon groups) and (B) at least one of Li, Na, K, Mg, Zn, Al and Ca elements. At least one reducing agent selected from the compounds contained above 3. A catalyst composition for hydrogenating an olefin compound, wherein the catalyst composition further comprises a component (C) in addition to the following component (A) and component (B). (A) At least one of the titanocene compounds represented by the following general formula (Formula 3): (However, R ⁵ and R ⁶ represent a group selected from hydrogen, a C _{1 to} C ₁₂ hydrocarbon group, an aryloxy group, an alkoxy group, a halogen group and a carbonyl group, and R ⁵ and R ⁶ are the same. Or R ¹ and R ² are hydrogen and C _1-
Represents a group selected from C ₁₂ hydrocarbon groups, R ¹ , R ²
May be the same or different. (Except when R ¹ and R ² are all hydrogen or all C _{1 to} C ₁₂ hydrocarbon groups) (B) At least one element of Li, Na, K, Mg, Zn, Al and Ca is contained. At least one reducing agent selected from the following compounds: (C) The fraction of the amount of olefinically unsaturated double bonds in the side chain to the total amount of olefinically unsaturated double bonds is 0.3 to 1
Is an olefinically unsaturated double bond-containing polymer. 4. An olefin compound characterized in that the catalyst composition contains the following components (A) and (B), or (A), (B) and (C), and further contains the following component (D). The catalyst composition for hydrogenation of. (A) at least one of the titanocene compounds represented by the following general formula (Formula 4): (However, R ⁵ and R ⁶ represent a group selected from hydrogen, a C _{1 to} C ₁₂ hydrocarbon group, an aryloxy group, an alkoxy group, a halogen group and a carbonyl group, and R ⁵ and R ⁶ are the same. Or R ¹ and R ² are hydrogen and C _1-
Represents a group selected from C ₁₂ hydrocarbon groups, R ¹ , R ²
May be the same or different. (Except when R ¹ and R ² are all hydrogen or all C _{1 to} C ₁₂ hydrocarbon groups) (B) Contain at least one element of Li, Na, K, Mg, Zn, Al and Ca. At least one reducing agent selected from the group of compounds (C), wherein the ratio of the amount of olefinically unsaturated double bonds in the side chain (C) to the total amount of olefinically unsaturated double bonds is 0.3 to 1
An olefinic unsaturated double bond-containing polymer, (D) an alcohol compound, an ether compound, a thioether compound, a ketone compound, a sulfoxide compound, a carboxylic acid compound, a carboxylic acid ester compound, an aldehyde compound, a lactone Compounds, amine compounds, amide compounds,
At least one polar compound selected from the group of nitrile compounds, epoxy compounds and oxime compounds. 5. The method for hydrogenating the olefinically unsaturated double bond in the compound by bringing the olefinically unsaturated double bond-containing compound (olefin compound) into contact with hydrogen in an inert organic solvent. A method for hydrogenating an olefin compound, which is carried out in the presence of the catalyst composition according to any one of 2 to 4. 6. The method for hydrogenating an olefin compound according to claim 5, wherein the olefin compound is a conjugated diene polymer or a copolymer of a conjugated diene and a vinyl aromatic hydrocarbon.