JPH05271327A - Hydrogenation of olefinic unsaturated polymer and hydrogenation catalyst - Google Patents

Abstract

PURPOSE:To hydrogenate an olefinic unsaturated polymer in high selectivity, hydrogenation rate and conversion and obtain a thermoplastic elastomer having excellent weather resistance, heat-resistance and oxidation resistance under mild hydrogenation condition by contacting the unsaturated polymer with hydrogen in the presence of a specific hydrogenation catalyst. CONSTITUTION:An olefinic unsaturated polymer is hydrogenated by contacting the unsaturated polymer with hydrogen in the presence of a hydrogenation catalyst composed of (A) a bis(cyclopentadienyl) transition metal compound of formula (M<1> is titanium, zirconium or hafnium; R<1> and R<2> are alkyl, aryl, etc.), (B) a ketone compound containing hydroxyl group such as hydroxyacetone and (C) an organic lithium compound such as methyllithium. The amount of lithium atom of the component C is >=1 equivalent based on 1 equivalent of the sum of the hydroxyl group and ketone-type carbonyl group of the component B.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for hydrogenating an olefinically unsaturated polymer and a hydrogenation catalyst. More specifically, the present invention relates to a hydrogenation method and a hydrogenation catalyst having high hydrogenation activity for imparting weather resistance, heat resistance, oxidation resistance and other properties to an olefinically unsaturated polymer.

[0002]

2. Description of the Related Art Olefinic unsaturated bond-containing polymers represented by conjugated diene polymers are widely industrially used as elastomers. However, the olefinically unsaturated bonds in these polymers are
While it is advantageously used for vulcanization and the like, it is a cause of impairing weather resistance and heat resistance, and it is also prone to the drawback that the use of the polymer is limited.

The inferior weather resistance and heat resistance are
It is significantly improved by hydrogenating the polymer to eliminate olefinically unsaturated bonds in the polymer chain. For this purpose, as a method of hydrogenating the olefinically unsaturated bond-containing polymer, nickel, platinum, a metal such as palladium, carbon, silica, a method of using a supported heterogeneous catalyst supported on a carrier such as alumina and ,nickel,
It is known to use a homogeneous catalyst obtained by reacting an organometallic compound such as cobalt or titanium with a reducing compound such as organoaluminum, organomagnesium or organolithium in a solvent.

[0004]

However, the former supported heterogeneous catalyst generally has low activity as compared with a homogeneous catalyst, and it is necessary to use a high temperature in order to carry out a hydrogenation (hereinafter sometimes referred to as hydrogenation) reaction. It requires severe conditions of high pressure.
In addition, since the hydrogenation reaction proceeds when the substance to be hydrogenated contacts with the catalyst, when the polymer is hydrogenated, the viscosity of the reaction system and the steric hindrance of the polymers are higher than those of the low molecular weight compounds. Under the influence of, it becomes difficult to contact with the catalyst. Therefore, in order to efficiently hydrogenate a polymer, a large amount of catalyst is required, which is uneconomical, and a hydrogenation reaction at a higher temperature and a higher pressure is required, so that decomposition or gelation of the polymer easily occurs. At the same time, the energy cost increases. Further, in the hydrogenation of a copolymer of a conjugated diene and a vinyl-substituted hydrocarbon, the aromatic nucleus portion is also usually hydrogenated,
There is a defect that it becomes difficult to selectively hydrogenate only the unsaturated double bond of the conjugated diene unit.

On the other hand, the latter homogeneous catalyst generally has a higher activity as compared with the supported heterogeneous catalyst because the hydrogenation reaction normally proceeds in a homogeneous system, and the amount of the catalyst used is small.
It has a feature that hydrogenation reaction can be performed at lower temperature and lower pressure.

Further, by selecting the hydrogenation conditions, it is possible to preferentially hydrogenate the unsaturated double bond of the conjugated diene unit of the copolymer of the conjugated diene and the vinyl-substituted aromatic hydrocarbon. However, a homogeneous catalyst has a problem that reproducibility is poor because the hydrogenation activity greatly changes depending on the reduced state of the catalyst, and it is difficult to obtain a certain highly hydrogenated polymer. Further, since the catalyst component is easily changed into an inactive substance by the impurities, the hydrogenation activity is lowered by the impurities in the reaction system, which also causes the hydrogenation by the homogeneous catalyst to be difficult to obtain reproducibility. The fact that a highly hydrogenated polymer cannot be obtained with good reproducibility is a major obstacle in industrially utilizing the hydrogenation reaction with a homogeneous catalyst for the purpose of improving the weather resistance and heat resistance of the polymer.

In addition, in the conventional hydrogenation of polymers using homogeneous catalysts, the rate of hydrogenation reaction cannot be said to be sufficiently high. In addition, the hydrogenation activity decreases due to the reduced state of the catalyst and impurities in the system, and the reaction rate also decreases, so there is a problem in industrially hydrogenating the polymer using a homogeneous catalyst.

Therefore, there is a strong demand for the development of a highly active hydrogenated catalyst which is unlikely to be affected by impurities in the reaction system and which can stably obtain a polymer having a high hydrogenation rate at a high speed regardless of the preparation conditions of the catalyst. Is the current situation.

The hydrogenation reaction using the bis (cyclopentadienyl) transition metal compound used in the present invention as one component of the catalyst component is already known [eg MF Sloa
n et al., J. Am. Chem. Soc., 85, 4014-4018 (1965); Y. T.
ajima et al., J. Org. Chem., 33, 1689-1690 (1968), JP-A-59-133203, JP-A-61-28507.
Issue bulletin, etc.]. However, even if these known methods are used, the above-mentioned problems cannot be solved. In addition, these publications do not disclose any technique that suggests a method for solving the problem.

The present invention has been made against the background of the above-mentioned conventional technical problems. Under the mild conditions, the olefinic unsaturated bond in the polymer chain is selectively hydrogenated at a high rate, and the An object of the present invention is to provide a hydrogenation method and a hydrogenation catalyst which are hardly affected by impurities and have extremely high activity and which can obtain a certain highly hydrogenated polymer.

[0011]

According to the present invention, the above objects and advantages of the present invention are as follows: (a) the following formula (1):

[0012]

[Chemical 2]

(Wherein M ¹ is a transition metal atom selected from the group consisting of titanium, zirconium and hafnium, and R ¹ and R ² are the same or different and are an alkyl group, an aryl group, an aralkyl group or an alkoxy group. , An aryloxy group, an acyloxyl group, a carbonyl ligand, a β-diketone ligand or a halogen atom)

A bis (cyclopentadienyl) transition metal compound represented by: (b) a hydroxyl group-containing ketone compound, and (c) an organolithium compound, and the hydroxyl group-containing ketone compound (b) has a hydroxyl group and ketonicity. The olefinically unsaturated polymer is brought into contact with hydrogen in the presence of a hydrogenation catalyst in which the lithium atom of the organic lithium compound (c) is 1 equivalent or more per 1 equivalent of the total amount of carbonyl groups. It is achieved by a method for hydrogenating an olefinically unsaturated polymer characterized by selectively hydrogenating the olefinically unsaturated bond of

Specific examples of the bis (cyclopentadienyl) transition metal compound which is the component (a) used in the present invention include bis (cyclopentadienyl) titanium dimethyl, bis (cyclopentadienyl) titanium diethyl, Bis (cyclopentadienyl) titanium di-n-
Butyl, bis (cyclopentadienyl) titanium di-
sec-butyl, bis (cyclopentadienyl) titanium dihexyl, bis (cyclopentadienyl) titanium dioctyl, bis (cyclopentadienyl) titanium dimethoxide, bis (cyclopentadienyl) titanium diethoxide, bis (cyclo Pentadienyl) titanium dibutoxide, bis (cyclopentadienyl)
Titanium diphenyl, bis (cyclopentadienyl)
Titanium di-m-tolyl, bis (cyclopentadienyl) titanium di-p-tolyl, bis (cyclopentadienyl) titanium di-2,4-xylyl, bis (cyclopentadienyl) titanium di-4-ethyl Phenyl, bis (cyclopentadienyl) titanium di-4-
Butylphenyl, bis (cyclopentadienyl) titanium di-4-hexylphenyl, bis (cyclopentadienyl) titanium diphenoxide, bis (cyclopentadienyl) titanium difluoride, bis (cyclopentadienyl) titanium dichloride, Bis (cyclopentadienyl) titanium dibromide, bis (cyclopentadienyl) titanium diiodide, bis (cyclopentadienyl) titanium dicarbonyl, bis (cyclopentadienyl) methyltitanium chloride, bis (cyclopentadienyl) ) Methoxytitanium chloride, bis (cyclopentadienyl) ethoxytitanium chloride, bis (cyclopentadienyl) isopropoxytitanium chloride, bis (cyclopentadienyl) phenoxytitanium chloride Chloride, bis (cyclopentadienyl) titanium dibenzyl, bis (cyclopentadienyl) titanium diacetate, bis (cyclopentadienyl) titanium diacetylacetonate,

Bis (cyclopentadienyl) zirconium dimethyl, bis (cyclopentadienyl) zirconium diethyl, bis (cyclopentadienyl) zirconium di-n-butyl, bis (cyclopentadienyl) zirconium di-sec-butyl , Bis (cyclopentadienyl) zirconium dihexyl, bis (cyclopentadienyl) zirconium dioctyl, bis (cyclopentadienyl) zirconium dimethoxide, bis (cyclopentadienyl) zirconium diethoxide, bis (cyclopentadienyl) ) Zirconium dibutoxide, bis (cyclopentadienyl) zirconium diphenyl, bis (cyclopentadienyl) zirconium di-m-tolyl, bis (cyclopentadienyl) zirconium di-p
-Tolyl, bis (cyclopentadienyl) zirconium di-2,4-xylyl, bis (cyclopentadienyl)
Zirconium di-4-ethylphenyl, bis (cyclopentadienyl) zirconium diphenoxide, bis (cyclopentadienyl) zirconium difluoride, bis (cyclopentadienyl) zirconium dichloride, bis (cyclopentadienyl) zirconium dibromide ,
Bis (cyclopentadienyl) zirconium diiodide, bis (cyclopentadienyl) zirconium dicarbonyl, bis (cyclopentadienyl) methyl zirconium chloride,

Bis (cyclopentadienyl) hafnium dimethyl, bis (cyclopentadienyl) hafnium diethyl, bis (cyclopentadienyl) hafnium di-
n-butyl, bis (cyclopentadienyl) hafnium di-sec-butyl, bis (cyclopentadienyl) hafnium dihexyl, bis (cyclopentadienyl) hafnium dimethoxide, bis (cyclopentadienyl)
Hafnium diethoxide, bis (cyclopentadienyl) hafnium dibutoxide, bis (cyclopentadienyl) hafnium diphenyl, bis (cyclopentadienyl) hafnium di-m-tolyl, bis (cyclopentadienyl) hafnium di-p- Trilyl, bis (cyclopentadienyl) hafnium-2,4-xylyl, bis (cyclopentadienyl) hafnium diphenoxide,
Bis (cyclopentadienyl) hafnium difluoride, bis (cyclopentadienyl) hafnium dichloride, bis (cyclopentadienyl) hafnium dibromide, bis (cyclopentadienyl) hafnium diiodide, bis (cyclopentadienyl) Hafnium dicarbonyl, bis (cyclopentadienyl) methyl hafnium chloride and the like can be mentioned. These compounds can be used alone or in combination.

Of these bis (cyclopentadienyl) transition metal compounds, the hydrogenation activity for the olefinic unsaturated bond in the polymer is high, and the unsaturated bond is satisfactorily selectively hydrogenated under mild conditions. More preferred are bis (cyclopentadienyl) titanium dimethyl, bis (cyclopentadienyl) titanium di-n-
Butyl, bis (cyclopentadienyl) titanium dichloride, bis (cyclopentadienyl) titanium diphenyl, bis (cyclopentadienyl) titanium di-
p-tolyl, bis (cyclopentadienyl) titanium dicarbonyl, bis (cyclopentadienyl) titanium dibenzyl, bis (cyclopentadienyl) isopropoxytitanium chloride, bis (cyclopentadienyl) zirconium dichloride, bis ( Cyclopentadienyl) zirconium dibromide, bis (cyclopentadienyl) zirconium diphenyl, bis (cyclopentadienyl) zirconium di-p-tolyl, bis (cyclopentadienyl) hafnium dichloride, bis (cyclopentadienyl) Hafnium dibromide, bis (cyclopentadienyl) hafnium diphenyl, bis (cyclopentadienyl) hafnium di-p-tolyl can be mentioned.

Component (b) is a hydroxyl group-containing ketone compound. The hydroxyl group-containing ketone compound is a compound having both a hydroxyl group and a ketonic carbonyl group in the molecule. As a specific example, hydroxyacetone,
4-hydroxy-2-butanone, 3-hydroxy-3-
Methyl-2-butanone, 5-hydroxy-2-butanone, diacetone alcohol, 4- (p-hydroxyphenyl) -2-butanone, 2-hydroxyacetophenone, 2'-hydroxyacetophenone, 3'-hydroxyacetophenone, 4 '. -Hydroxyacetophenone,
4'-hydroxy-3'-methoxyacetophenone, 2
-Hydroxyphenyl ethyl ketone, 4'-hydroxypropiophenone, 2 ', 4'-dihydroxyacetophenone, 2', 5'-dihydroxyacetophenone,
2 ', 6'-dihydroxyacetophenone, 3', 5'-
Dihydroxyacetophenone, 2 ', 3', 4'-trihydroxyacetophenone, 2-hydroxybenzophenone, 4-hydroxybenzophenone, 2-hydroxy-
4-methoxybenzophenone, 2-hydroxy-4-n
-Octyloxybenzophenone, 2,2'-dihydroxybenzophenone, 2,4-dihydroxybenzophenone, 4,4'-dihydroxybenzophenone, 2,2 '
-Dihydroxy-4-methoxybenzophenone, 2,4,
Preferred examples include 4'-trihydroxybenzophenone and benzoin.

Next, specific examples of the organic lithium as the component (c) include methyllithium, ethyllithium, and n-.
Propyl lithium, n-butyl lithium, sec-butyl lithium, t-butyl lithium, n-hexyl lithium, phenyl lithium, p-tolyl lithium, xylyl lithium, 1,4-dilithiobutane, alkylenedilithium, butyllithium and divinylbenzene. Reaction products with and the like. In addition to these low molecular weight organolithium compounds, a living polymer having lithium at the terminal can be used as the organolithium compound of the component (c).

Particularly preferred among these are n-butyllithium, sec-butyllithium, t-butyllithium, phenyllithium or living polymers having lithium at the terminal.

The hydrogen catalyst used in the present invention comprises the above-mentioned components (a), (b) and (c), and if necessary, the following component (d) can be used as one component.

As the component (d), a reducing organometallic compound selected from the group consisting of aluminum compounds, zinc compounds and magnesium compounds is used. Specific examples of these include aluminum compounds such as trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, triphenyl aluminum, diethyl aluminum chloride, ethyl aluminum dichloride, methyl aluminum sesquichloride, ethyl aluminum sesquichloride, diethyl aluminum hydride, diisobutyl aluminum hydride. , Tri (2-ethylhexyl) aluminum, aluminum triisopropoxide, aluminum tri-t-butoxide, diethylaluminum ethoxide and the like.

Examples of the zinc compound include diethyl zinc, bis (cyclopentadienyl) zinc, diphenyl zinc and the like.

Further, as the magnesium compound, for example, dimethyl magnesium, diethyl magnesium, methyl magnesium bromide, methyl magnesium chloride,
Ethyl magnesium bromide, ethyl magnesium chloride, phenyl magnesium bromide, phenyl magnesium chloride, t-butyl magnesium chloride and the like can be mentioned. In addition to these, as the component (d), a compound containing two or more reducing metals such as lithium aluminum hydride can be mentioned.

Taking into consideration the difficulty of industrial availability and the ease of handling, triethylaluminum, triisobutylaluminum, diethylaluminum chloride, ethylaluminum dichloride, aluminum triisopropoxide and aluminum tri-t-butoxide are preferred.

The composition of the catalyst used in the present invention preferably has a molar ratio of catalyst (a) component / catalyst (b) component of 1 /.
It is 0.5 or more, more preferably 1/1 to 1/20, and further preferably 1 / 1.5-1 / 15. If the amount of the catalyst (b) component is less than 0.5 mol per 1 mol of the component (a), the catalyst activity will be insufficient, and hydrogenation of the polymer under mild conditions tends to be difficult.

The catalyst (a) component / catalyst (c) component molar ratio is preferably 1/1 to 1/50, more preferably 1/3 to 1/40, and further preferably 1/3 to 1 / 3
It is 5. The catalyst (c) component is relative to 1 mol of the component (a),
If it is less than 1 mol, the hydrogenation reaction is very slow, while if it exceeds 50 mol, the catalytic activity of hydrogen is retained, but gelation of the polymer and side reactions are likely to occur, which is not preferable.

Further, the ratio of the catalyst (b) component to the catalyst (c) component is such that the lithium atom of the component (c) is 1 equivalent or more per the total equivalent of the hydroxyl group and the ketonic carbonyl group of the component (b). Is.

Preferably, the lithium atom of the component (c) /
The equivalent ratio of the total of the hydroxyl group and the ketonic carbonyl group of the component (b) is 2 or less, and more preferably 1.0 to
1.6, more preferably 1.0 to 1.5,
Particularly preferably, it is 1.0 to 1.4. A compound containing a total of two hydroxyl groups and ketonic carbonyl groups in the molecule has 1 equivalent of 2 equivalents, and a compound containing three of them has 1 equivalent of 3 equivalents.

Further, the molar ratio of the component (a) / the component (d) is preferably 1/20 or less, more preferably 1/1 to 1/18, and further preferably 1/2 to 1/15.
Is. The catalyst (d) component is 2 per 1 mol of the component (a).
If it is added in an amount of more than 0 mol, the catalytic activity will rather be lowered, and it will be difficult to obtain a highly hydrogenated polymer.

Further, the preferred amount of the catalyst of the present invention is 0.005 to 50.0 mmol in terms of component (a) based on 100 g of the polymer to be hydrogenated. If it is less than 0.005 mmol, the hydrogenation efficiency is poor, while if it exceeds 50 mmol, hydrogenation is possible, but it is uneconomical to use the catalyst more than necessary, and removal of the catalyst residue from the polymer becomes complicated. It becomes a disadvantage. A more preferable range is (a)
It is 0.01 to 5 mmol in terms of components.

By using the above-mentioned catalyst of the present invention, it is possible to obtain a constant highly hydrogenated polymer regardless of the catalyst preparation conditions and the state of the system.

The olefinically unsaturated polymer to be hydrogenated according to the present invention includes all polymers having an olefinic carbon-carbon unsaturated double bond in the polymer main chain or side chain. As a preferred representative example,
Examples thereof include a conjugated diene polymer or a random, block or graft polymer of a conjugated diene and an olefin.

Examples of the conjugated diene polymer include a conjugated diene homopolymer and a conjugated diene, or a copolymer obtained by copolymerizing at least one conjugated diene or at least one conjugated diene and at least one olefin copolymerizable with the conjugated diene. To be done.

The conjugated diene used for producing the conjugated diene polymer generally includes a conjugated diene having 4 to 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-hexadiene, 4 ,
5-diethyl-1,3-octadiene, 3-butyl-1,
Examples include 3-octadiene and chloroprene.

1,3-Butadiene and isoprene are particularly preferable from the standpoint of obtaining an elastomer which can be industrially advantageously developed and has excellent physical properties, and elastomers such as polybutadiene, polyisoprene and butadiene / isoprene copolymer are used in the present invention. Is particularly preferred. In this polymer, the microstructure of the polymers is not particularly limited, and any of them can be suitably used as a hydrogenation target.

On the other hand, the method of the present invention is particularly preferably used for hydrogenating a copolymer obtained by copolymerizing at least one conjugated diene and at least one olefin copolymerizable with the conjugated diene.

Suitable conjugated dienes for use in the production of this copolymer include the conjugated dienes mentioned above. Examples of the olefin include all monomers copolymerizable with the conjugated diene, and vinyl-substituted aromatic hydrocarbons are particularly preferable.

Copolymers of conjugated dienes and vinyl-substituted aromatic hydrocarbons are particularly important for obtaining industrially useful and valuable elastomers and thermoplastic elastomers. Specific examples of the vinyl-substituted aromatic hydrocarbon used for producing this copolymer include styrene, t-butylstyrene, α-methylstyrene, p-methylstyrene, divinylbenzene, 1,1-diphenylethylene, N, N-.
Examples thereof include dimethyl-p-aminoethylstyrene, N, N-diethyl-p-aminoethylstyrene and vinylpyridine. Of these, styrene and α-methylstyrene are particularly preferable. As specific examples of the copolymer, butadiene-styrene copolymer, isoprene-styrene copolymer, butadiene-α-methylstyrene copolymer and the like are most preferable because they give hydrogenated copolymers having high industrial value.

In this copolymer, the monomers include random copolymers, tapering block copolymers, full block copolymers, graft copolymers, which are statistically distributed throughout the polymers.

To obtain an industrially useful thermoplastic elastomer, the vinyl-substituted aromatic hydrocarbon content is 5-9.
5% by weight is preferred. In addition, the vinyl bond of the conjugated diene unit is preferably 10% by weight or more of the entire conjugated diene unit because of excellent polymer performance after hydrogenation.

The polymer used in the hydrogenation reaction of the present invention generally has a molecular weight of about 1,000 to 1,000,000, and is a so-called branched polymer which is coupled with a coupling agent in addition to the linear type. Type, radial or star block polymers are included.

Specific examples of the coupling agent include divinylbenzene, tetrachlorosilane, methyldichlorosilane, butyltrichlorosilane, (dichloromethyl) trichlorosilane, (dichlorophenyl) trichlorosilane, 1,2-bis (trichlorosilyl) ethane, Hexachlorodisilane, 1,2,3,4,7,7-hexachloro-
6-methyldichlorosilyl-2-norbornene, octachlorotrisiloxane, trichloromethyltrichlorosilane, tetrachlorotin, butyltrichlorotin, tetrachlorogermanium, 1,2-dibromoethane, epoxidized linseed oil, tolylene diisocyanate, etc. Be done.

In living anionic polymerization, a polymer whose terminal is modified with a polar group and a polymer whose terminal is modified with a polar group by other means are also included. Examples of the polar group to be modified include hydroxyl group, carboxyl group, ester group, isocyanate group, urethane group, amide group, urea group and thiourethane group.

Polymers produced by any other known polymerization method such as anionic polymerization method, cationic polymerization method, coordination polymerization method, radical polymerization method or solution polymerization method, emulsion polymerization method can be used.

Further, a polymer of a cyclic olefin obtained by ring-opening polymerization using a metathesis catalyst such as molybdenum or tungsten is also included in the polymer having an olefinic unsaturated bond used in the present invention.

Specific examples of the monomer constituting this polymer include cyclobutene, cyclopentene, cyclooctene, 1,5-cyclooctadiene, 1,5,9-cyclododecatriene, norbornene and 5-methyl-norbornene. Such as cycloalkene; methyl 5-norbornene-2-carboxylate, ethyl 5-norbornene-2-carboxylate, phenyl 5-norbornene-2-carboxylate, 2-
Methyl-5-norbornene-2-carboxylate, 3
-Butyl-5-norbornene-2-carboxylate, dimethyl 5-norbornene-2,3-dicarboxylate, cyclohexyl 5-norbornene-2-carboxylate, aryl 5-norbornene-2-carboxylate, 5-
Norbornen-2-ylacetate, 5-norbornene-2-nitrile, 3-methyl-5-norbornene-2-
Nitrile, 2,3-dimethyl-5-norbornene-2,3
-Dinitrile, 5-norbornene-2-carboxylic acid amide, N-methyl-5-norbornene-2-carboxylic acid amide, N, N-diethyl-5-norbornene-2-carboxylic acid amide, N, N-dimethyl-2 -Methyl-5-norbornene-2,3-dicarboxylic acid amide, 5-norbornene-2,3-dicarboxylic acid anhydride (hymic acid anhydride), 2,3-dimethyl-5-norbornene-2,3-dicarboxylic acid imide , N-phenyl-2-methyl-5-norbornene-2,3-dicarboxylic acid imide, 5-methyl-5-carboxycyclohexylbicyclo [2.2.
1.]-2-heptene, 5-methyl-5-carboxy (4-t-butylcyclohexyl) bicyclo [2.2.
. 1] - 2-heptene, 8-methyl-8-carboxy-cyclohexyl-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10]
-3-Dodecene, 5-methyl-5-carboxytricyclo [5.2.1.0 ^2,6 ] decyl-8'-bicyclo [2.2.
Norbornene derivatives such as 1.]-2-heptene can be used.

The bis (cyclopentadienyl) transition metal compound of the component (a), the hydroxyl group-containing ketone compound of the component (b) and the organolithium compound of the component (c) described above are used in the present invention. Catalyst and the above (a)
The catalysts of the present invention containing the reducing organometallic compound of the components (c) and (d) each have good reproducibility and high hydrogenation activity.

The respective components of these catalysts may be mixed in advance and then added to the hydrogenation reaction system, or may be separately added to the system in any order. For example, a method of adding the component (b) to a living polymer having lithium at the terminal and reacting it, and then adding the component (a) or the component in which the component (a) and the component (d) are mixed in advance and hydrogenating. Alternatively, a reaction product obtained by previously reacting the component (b) and the component (c) is added to the system, and another mixture of the component (a) or the component (a) and the component (d) is added to the system and water is added. The water addition reaction can be carried out by the addition method.

When the respective components are mixed in advance, it is desirable to carry out under an inert atmosphere. Here, the inert atmosphere means an atmosphere that does not react with any participant in the hydrogenation reaction such as nitrogen, helium, neon, or argon. Air or oxygen is not preferable because it oxidizes the catalyst and deactivates the catalyst. In addition, when the catalyst is mixed in advance, it can be carried out under a hydrogen atmosphere in addition to the inert atmosphere.

The hydrogenation reaction of the present invention is carried out in a state where the olefinic unsaturated polymer is dissolved in a hydrocarbon solvent, or after the olefinic unsaturated polymer is produced by polymerization in a hydrocarbon solvent, Subsequent hydrogenation can also be carried out. Here, the hydrocarbon solvent includes aliphatic hydrocarbons such as pentane, hexane, heptane, and octane; aliphatic hydrocarbons such as cyclopentane, methylcyclopentane, and cyclohexane; aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene. Hydrogen can be used. These hydrocarbon solvents may contain ethers such as diethyl ether, tetrahydrofuran and dibutyl ether in an amount of 20% by weight or less.

The polymer concentration for carrying out the hydrogenation reaction of the present invention is not particularly limited, but is usually 1 to 30% by weight, preferably 3 to 20% by weight. The hydrogenation reaction is carried out by adding the above-mentioned hydrogenation catalyst under an atmosphere of an inert gas such as nitrogen or argon or hydrogen, and then supplying hydrogen under pressure at a pressure of 1 to 100 kg / cm ² , and further adding a polymer solution. Is maintained at a predetermined temperature and is carried out with or without stirring.

The pressure of hydrogen used in the hydrogenation reaction is
It is preferably 1 to 100 kg / cm ² G, more preferably 4 to 20 kg / cm ² G. If it is less than 1 kg / cm ² G, the hydrogenation rate becomes slow, while if it exceeds 100 kg / cm ² G, gelation of the polymer and unnecessary side reactions are likely to occur together, which is not preferable.

The temperature range suitable for the hydrogenation reaction is
It is 0 to 150 ° C, and if it is less than 0 ° C, the activity of the catalyst is lowered, and the hydrogenation rate is slow, and a large amount of the catalyst is required, which is not economical. And hydrogenation of the aromatic nucleus portion easily occurs, and the hydrogenation selectivity decreases, which is not preferable.
It is preferably in the range of 20 to 140 ° C, and more preferably in the range of 70 to 130 ° C.

The hydrogenation reaction time of the present invention is 1 minute to 10 minutes.
The reaction time becomes shorter as the amount of hydrogenation catalyst increases and the hydrogen pressure increases. The hydrogenation reaction of the present invention can be carried out by either a batch method or a continuous method. By the hydrogenation reaction of the present invention, a polymer in which 80% or more, preferably 90% or more of olefinic unsaturated double bonds are hydrogenated can be obtained. However, the hydrogenation of the double bond of the aromatic nucleus, when present, is less than 5% and virtually no hydrogenation. In addition, the hydrogenation reaction of the present invention hardly causes the molecular cleavage of the polymer.

Any proportion of unsaturated double bonds in the polymer can be hydrogenated by the method of the present invention. The hydrogenation catalyst of the present invention can also be used for hydrogenating olefins such as styrene. The polymer hydrogenated by the method of the present invention, the catalyst residue is removed from the polymer solution if necessary, an antioxidant is added, the polymer solution is poured into hot water with steam, the solvent A method of recovering the polymer in a crumb form by recovering by steam distillation, a method of allowing the polymer solution to flow on a heating roll and evaporating a solvent to recover the polymer, or a method of recovering the polymer solution with a polar solvent such as alcohol or acetone. It can be isolated from the polymer solution by, for example, a method in which the polymer is poured into a solvent to precipitate and recover the polymer.

In the hydrogenation method of the present invention, since the amount of the catalyst used is small, the catalyst residue is small, and the catalyst residue has little influence on the weather resistance and heat resistance of the polymer. Can be excluded.

[0059]

According to the present invention, by improving the drawbacks of the conventional homogeneous hydrogenation catalyst, and by using the catalyst of the present invention containing a bis (cyclopentadienyl) transition metal compound and a hydroxyl group-containing ketone compound, A highly hydrogenated polymer that is not easily affected by impurities in the system, has a high hydrogenation activity, and is stable at a high speed can be provided.

[0060]

The present invention will be described in more detail below with reference to examples, but the present invention is not limited thereto. In addition, the vinyl bond content of the conjugated diene-based polymer in the examples, using infrared absorption spectrum, the Hampton method [RR Hampton, Anal. Chem., Vol. 29, page 923,
(1949)].

Example 1 After charging 5 kg of degassed and dehydrated cyclohexane and 1 kg of 1,3-butadiene into a 10 l autoclave,
Tetrahydrofuran (15 g) and n-butyllithium (1.1 g) were added to carry out temperature-rise polymerization from a polymerization temperature of 50 ° C. After the conversion rate is almost 100%, the living Li
When the amount was measured, it was 13.4 mmol. Into this system, 1.46 g of 2-hydroxy-4-methoxybenzophenone was added to the autoclave and stirred for 10 minutes. From the change in color of the polymer liquid, it was confirmed that there was no polymer-terminated lithium as a living anion. Next, 0.20 g of n-butyllithium was added to the system, and 0.40 g of bis (cyclopentadienyl) was added.
Titanium dichloride and 1.16 g of diethylaluminum chloride dissolved in 10 ml of toluene were mixed in advance under a nitrogen atmosphere, and after stirring,
Hydrogen gas was supplied at a pressure of 8 kg / cm ² G, and the reaction was carried out at 90 ° C. for 3 hours. The hydrogenation rate of the obtained hydrogenated polymer was 94%, the 1,2-vinyl bond content of the polymer before hydrogenation was 41%, and the number average molecular weight was 100,000.

Comparative Example 1 Polymerization and hydrogenation reaction were carried out in the same manner as in Example 1 except that 2-hydroxy-4-methoxybenzophenone was not added. The hydrogenation rate of the obtained hydrogenated polymer was 56%.

Example 2 A 10-liter autoclave was charged with 5 kg of degassed and dehydrated cyclohexane, 300 g of styrene and 700 g of 1,3-butadiene, 15 g of tetrahydrofuran and 1.1 g of n-butyllithium were added, and the polymerization temperature was 50.
Polymerization at elevated temperature from ° C was performed. When the amount of living Li was measured after the conversion reached almost 100%, it was 13.5 mmol. 2-Hydroxy-4-n-octyloxybenzophenone (1.92 g) and n-butyllithium (0.13 g) were added to the system, and the mixture was stirred for 20 minutes. Next, 0.53 g of bis (cyclopentadienyl) titanium dibenzyl dissolved in 20 ml of toluene was charged,
Hydrogen gas was supplied at a pressure of 8 kg / cm ² G, and the reaction was carried out at 90 ° C. for 4 hours. The hydrogenation rate of the obtained hydrogenated polymer was 92%, the 1,2-vinyl bond content of the polymer before hydrogenation was 39%, and the number average molecular weight was 97,000.

Example 3 Polymerization was carried out in the same manner as in Example 1, and after the conversion reached about 100%, the amount of living Li was measured and found to be 13.4 mmol. To this system, 1.02 g of diacetone alcohol and 0.49 g of n-butyllithium were added, and 0.52 g of bis (cyclopentadienyl) titanium dichloride and 1.51 g of diethylaluminum chloride dissolved in 10 ml of toluene were added to a nitrogen atmosphere. The components premixed below were charged into the system, and after stirring, hydrogen gas was supplied at a pressure of 8 kg / cm ² G and the mixture was heated at 90 ° C. for 4 hours.
A time reaction was performed. The hydrogenation rate of the obtained hydrogenated polymer was 9
4%, 1,2-vinyl bond content of the polymer before hydrogenation is 4
0% and the number average molecular weight were 100,000.

Example 4 Polymerization was carried out in the same manner as in Example 2, and the living Li content was measured after the conversion reached about 100%.
It was millimole. Add 0.24g of water to this system and add 2
Stir for 0 minutes. From the change in color of the polymer liquid, it was confirmed that there was no polymer-terminated lithium as a living anion. The number average molecular weight of the polymer obtained at this time was 1030,000, but 100 g of styrene was further added, and it was confirmed that the color of styryllithium did not appear and that the molecular weight distribution did not change before and after the addition of styrene.

Then 2-hydroxy-4-methoxybenzophenone 1.57 dissolved in 20 ml cyclohexane.
g and n-butyllithium 0.93 g were preliminarily reacted for 20 minutes under a nitrogen atmosphere, charged with a reaction product, and further dissolved in 0.36 g of bis (cyclopentadienyl) titanium dichloride and 10 ml of toluene of 1.05 g. The components prepared by mixing diethylaluminum chloride in advance under a nitrogen atmosphere were placed in an autoclave and stirred. Hydrogen gas was supplied at a pressure of 8 kg / cm ² G, and
The reaction was carried out at ℃ for 4 hours. The hydrogenation rate of the obtained hydrogenated polymer was 93%, and the 1,2-vinyl bond content of the polymer before hydrogenation was 39%.

Example 5 Polymerization and hydrogenation reaction were carried out in the same manner as in Example 4 except that 1.57 g of 2-hydroxy-4-methoxybenzophenone was changed to 0.99 g in Example 4. The hydrogenation rate of the obtained hydrogenated polymer was 61%.

[0068]

The hydrogenated polymer obtained by the present invention is
It is used as a thermoplastic elastomer or thermoplastic resin with excellent weather resistance, heat resistance and oxidation resistance.It is also used by adding additives such as UV absorbers, oils and primers, and by blending with other elastomers and resins. It is industrially useful. Further, the olefinic unsaturated bond-containing polymer used in the present invention can be selectively hydrogenated at a very high rate and a high conversion rate under mild conditions.

Front page continued (72) Inventor Yasuhiko Takemura 2-11-24 Tsukiji, Chuo-ku, Tokyo Japan Synthetic Rubber Co., Ltd.

Claims (3)

[Claims] 1. (a) The following formula (1): (Wherein M ¹ is a transition metal atom selected from the group consisting of titanium, zirconium and hafnium, and R ¹ and R ² are the same or different and are an alkyl group, an aryl group, an aralkyl group, an alkoxy group or an aryloxy group. , An acyloxyl group, a carbonyl ligand, a β-diketone ligand or a halogen atom), a bis (cyclopentadienyl) transition metal compound, (b) a hydroxyl group-containing ketone compound, and (c) an organic compound. In the presence of a hydrogenation catalyst comprising a lithium compound and having a ratio of 1 equivalent or more of lithium atoms of the organolithium compound (c) per 1 equivalent of the total of hydroxyl groups and ketonic carbonyl groups of the hydroxyl group-containing ketone compound (b), Contacting an olefinically unsaturated polymer with hydrogen to produce the olefinically unsaturated polymer Olefinically unsaturated polymer hydrogenation method, characterized in that allowed to selective hydrogenation of olefinically unsaturated bond. 2. The hydrogenation catalyst according to any one of (a) and (b) above.
In addition to the components (c) and (c), the component (d) further contains a reducing organometallic compound selected from the group consisting of aluminum compounds, zinc compounds and magnesium compounds.
The method described in. 3. The hydrogenation catalyst according to claim 1 or 2.