JP3328916B2 - Method for hydrogenating polymer containing olefinically unsaturated bond and hydrogenation catalyst - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for hydrogenating polymers containing olefinically unsaturated bonds and to a hydrogenation catalyst. More specifically, the present invention relates to a hydrogenation method for obtaining a hydride having properties such as weather resistance, heat resistance and oxidation resistance from a polymer containing an olefinically unsaturated bond, and a hydrogenation catalyst having high hydrogenation activity.

[0002]

2. Description of the Related Art Olefinically unsaturated bond-containing polymers represented by conjugated diene polymers are widely and industrially used generally as elastomers and the like. However, the olefinically unsaturated bonds in these polymers
Although it is advantageously used for vulcanization and the like, it is a cause of impairing weather resistance, heat resistance, and the like, and has a drawback of limiting the applications of polymers.

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

[0004]

However, the former supported heterogeneous catalyst generally has lower activity than the homogeneous catalyst, and requires a high temperature to perform a hydrogenation (hereinafter sometimes referred to as hydrogenation) reaction. Requires high pressure, intense conditions.
In addition, the hydrogenation reaction proceeds when the product to be hydrogenated comes into contact with the catalyst, so when hydrogenating a polymer, the viscosity of the reaction system and the steric hindrance of the polymer are lower than when hydrogenating a low molecular weight compound. And contact with the catalyst becomes difficult. Therefore, in order to hydrogenate the polymer efficiently, a large amount of catalyst is required, which is uneconomical, and a higher temperature, high pressure hydrogenation reaction is required, so that decomposition and gelation of the polymer are likely to occur. At the same time, energy costs increase. In the hydrogenation of a copolymer of a conjugated diene and a vinyl-substituted hydrocarbon, usually, an aromatic nucleus is also hydrogenated,
There is a disadvantage that it is difficult to selectively hydrogenate only the unsaturated double bond of the conjugated diene unit.

[0005] On the other hand, the latter homogeneous catalyst usually has a higher activity and a smaller amount of catalyst used than the supported heterogeneous catalyst because the hydrogenation reaction usually proceeds in a homogeneous system.
There is a feature that the hydrogenation reaction can be performed at lower temperature and lower pressure.

If hydrogenation conditions are selected, it is also possible to preferentially hydrogenate unsaturated double bonds of conjugated diene units of a copolymer of a conjugated diene and a vinyl-substituted aromatic hydrocarbon. However, the homogeneous catalyst has a problem that reproducibility is poor because the hydrogenation activity greatly changes depending on the reduction state of the catalyst, and it is difficult to obtain a constant high hydrogenated polymer. Further, since the catalyst component is liable to be changed into an inert substance by impurities, the hydrogenation activity is reduced by impurities in the reaction system. This also causes the hydrogenation by the homogeneous catalyst to have difficulty in obtaining reproducibility. The inability to obtain a highly hydrogenated polymer with good reproducibility is a major obstacle to industrial use of a hydrogenation reaction with a homogeneous catalyst for the purpose of improving the weather resistance and heat resistance of the polymer.

Further, in the conventional hydrogenation of a polymer with a homogeneous catalyst, the rate of the hydrogenation reaction cannot be said to be sufficiently high. In addition, the hydrogenation activity is reduced due to the reduced state of the catalyst and impurities in the system, and the reaction rate is further reduced. Therefore, there is a problem in industrially hydrogenating a polymer using a homogeneous catalyst.

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

The hydrogenation reaction using a bis (cyclopentadienyl) transition metal compound as one component of the catalyst component used in the present invention is already known [for example, MF Sl]
Oan et al., J. Am. Chem. Soc., 85 , 40.
14-4018 (1965); Y. Tajima et al.
J. Org. Chem., 33 , 1689-1690.
(1968), JP-A-59-133203, JP-A-61-28507, 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 suggesting a method for solving the problem.

The present invention has been made on the background of the above-mentioned conventional technical problems, and selectively hydrogenates olefinically unsaturated bonds in a polymer chain at a high reaction rate under mild conditions,
It is an object of the present invention to provide a hydrogenation method and a hydrogenation catalyst having an extremely high activity, which are hardly affected by impurities in a hydrogenation method and a system in which a desired highly hydrogenated polymer is obtained.

[0012]

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

[0013]

Embedded image

(Where 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 , An allyloxy group, an acyloxyl group, a carbonyl ligand, a β-diketone ligand or a halogen atom)

Bis (cyclopentadienyl) transition metal compound represented by [0015], and is formed from (b) a lactone compound, at least one compound selected from the group consisting of lactam compounds and epoxy compounds and (c) an organolithium compound (B) lactone ring or lactone of component
When the equivalent ratio of the lithium atom of the tom ring / (c) component is 1 or less
Or epoxy group of component (b) / component of (c)
Hydrogenation catalysts having an equivalent ratio of lithium atoms of 2 or less
In the presence of the hydrogenation catalyst, a polymer containing an olefinic unsaturated bond contacted with hydrogen, the olefinic unsaturation, characterized in that allowed to selectively hydrogenate the olefinic unsaturated bond Achieved by a method for hydrogenating the containing polymer.

Hereinafter, the present invention will be described in detail, but the objects, configurations and effects of the present invention will be more apparent.

Specific examples of the bis (cyclopentadienyl) transition metal compound of the above formula (1), which is the component (a) used in the catalyst of the present invention, include bis (cyclopentadienyl) titanium dimethyl and bis (cyclopentadienyl) titanium dimethyl. 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 (cyclopentadiene) (Enyl) 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-ethylphenyl, 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) titaniumdiiodide, bis (cyclo (Pentadienyl) titanium dicarbonyl, bis (cyclopentadienyl) methyltitanium chloride, bis (cyclopentadienyl) methoxytitanium chloride, bis (cyclopentadienyl) ethoxytitanium chloride, bis (cyclopentadienyl) isopropoxy Titanium chloride, bis (cyclopentadienyl) phenoxytitanium 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- Tolyl, 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) methylhafnium chloride and the like can be mentioned. These compounds can be used alone or in combination.

Among these bis (cyclopentadienyl) transition metal compounds, the hydrogenation activity for the olefinically unsaturated bond in the polymer is high, and the unsaturated bond is favorably 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.

The component (b) used in the catalyst of the present invention is at least one compound selected from the group consisting of lactone compounds, lactam compounds and epoxy compounds.

Specific examples of the lactone compound include β-propiolactone, γ-butyrolactone, ε-caprolactone, △ α, β-croton lactone, γβ, γ-croton lactone, coumarin, phthalide, α-pyrone, sydnon,
Fluoran and the like. Among them, β-propiolactone, γ-butyrolactone, ε-caprolactone, coumarin and the like are preferable.

Specific examples of the lactam compound include β-propiolactam, 2-pyrrolidone, 2-piperidone, ε
-Caprolactam, n-heptane lactam, 8-octane lactam, 9-nonane lactam, 10-decane lactam, 2-quinolone, 1-isoquinolone, oxindole, isoindigo, isatin, hydantoin, 4-quinolidinone and the like. Among them, β-propiolactam, 2-pyrrolidone, 2-piperidone, ε-caprolactam and the like are preferable.

Specific examples of epoxy compounds include 1,3-
Butadiene monoxide, 1,3-butadiene oxide, 1,2-butylene oxide, 2,3-butylene oxide, cyclohexene oxide, 1,2-epoxycyclododecane, 1,2-epoxydecane, 1,2-epoxyeicosane 1,2-epoxyheptane, 1,2-epoxyhexadecane, 1,2-epoxyoctadecane, 1,2-
Epoxy octane, ethylene glycol diglycidyl ether, 1,2-epoxytetradecane, hexamethylene oxide, isobutylene oxide, 1,7-octadiene diepoxide, 2-phenylpropylene oxide,
Propylene oxide, trans-stilbene oxide,
Styrene oxide, epoxidized 1,2-polybutadiene, epoxidized linseed oil, glycidyl methyl ether,
Examples include glycidyl n-butyl ether, glycidyl allyl ether, glycidyl methacrylate, and glycidyl acrylate. Among them, 1,3-butadiene oxide, 2,3-butylene oxide, ethylene glycol diglycidyl ether, 1,2-epoxytetradecane, propylene oxide, styrene oxide, epoxidized linseed oil, epoxidized 1,2-polybutadiene and the like are particularly preferable. preferable.

Specific examples of the organic lithium as the component (c) used in the catalyst of the present invention include methyl lithium,
Ethyl lithium, 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, A reaction product of butyl lithium and divinylbenzene is exemplified. In addition to these low molecular weight organic lithium compounds, living polymers having a terminal lithium can be used as the organic lithium compound of the component (c).

Particularly preferred among these are n-butyllithium, sec-butyllithium, t-butyllithium, phenyllithium and living polymers having a terminal lithium.

The hydrogenation catalyst used in the present invention is formed from the above-mentioned components (a), (b) and (c). If necessary, the following component (d) can be further used as one component.

As the component (d), a reducing organic metal compound selected from the group consisting of an aluminum compound, a zinc compound and a magnesium compound is used. Specific examples of these include, as aluminum compounds, trimethylaluminum, triethylaluminum, triisobutylaluminum, triphenylaluminum, diethylaluminum chloride, ethylaluminum dichloride, methylaluminum sesquichloride, ethylaluminum sesquichloride, diethylaluminum hydride, diisobutylaluminum 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, dimethylmagnesium, diethylmagnesium, methylmagnesium bromide, methylmagnesium 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, a compound containing two or more kinds of reducing metals such as lithium aluminum hydride as the component (d) can also be mentioned.

Taking into account the degree of industrial availability and 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 is preferably such that the molar ratio of the catalyst (a) component / catalyst (b) component is 1 / 0.5 or a value smaller than this value, more preferably. 1 / 1.5-1 / 50, more preferably 1
/ 2 to 1/30. Such a range is preferable because the catalyst activity is maintained and the hydrogenation of the polymer under mild conditions is more easily performed.

The molar ratio of the catalyst (a) component / catalyst (c) component is preferably 1/1 to 1/40, more preferably 1/2 to 1/35, and further preferably 1/3 to 1/35. / 3
0. The above range is preferable from the viewpoint of maintaining the activity of the catalyst, gelling with a polymer, and suppressing other side reactions.

When the catalyst (b) component is a lactone compound or a lactam compound, the ratio of the catalyst (b) component to the catalyst (c) component is determined by the ratio of the lactone ring or lactam ring / (c) component of the lactone compound of the component (b). Equivalent ratio of lithium atoms
In state, and are 1 or less, the good Mashiku 0.5 to 0.75, more preferably from 0.5 to 0.65, particularly preferably 0.
5 to 0.6. One mole of a lactone compound or a lactam compound containing one lactone ring or lactam ring in the molecule is equivalent to 2 equivalents, and 1 mole of the compound containing two is equivalent to 4 equivalents.

When the catalyst (b) component is an epoxy compound,
The ratio of the catalyst (b) component to the catalyst (c) component is represented by an equivalent ratio of the epoxy group of the component (b) / the lithium atom of the component (c) .
2 below der is, the good Mashiku 1.01-1.5, more preferably from 1.01 to 1.3, particularly preferably 1.01
~ 1.2. One mole of an epoxy compound containing one epoxy group in the molecule is equivalent to one equivalent, and one mole of a compound containing two epoxy groups is equivalent to two equivalents.

Further, the molar ratio of the catalyst (a) component / catalyst (d) component is preferably 1/20 or a value larger than this value from the viewpoint of catalytic activity, more preferably 1/1 to 1/1 /. 18, more preferably 1/2 to 1/15
It is.

Further, the preferred amount of the catalyst of the present invention is 0.005 to 5 in terms of the component (a) per 100 g of the polymer to be hydrogenated in consideration of hydrogenation efficiency and economy.
0.0 mmol. A more preferred range is 0.01 to 5 mmol in terms of the component (a).

By using the above catalyst of the present invention, it is possible to obtain a constant high hydrogenated polymer.

The polymer having an olefinically unsaturated bond 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. . Preferred representative examples include a conjugated diene polymer or a random, block or graft polymer of a conjugated diene and an olefin.

The conjugated diene polymer includes a conjugated diene homopolymer and a copolymer obtained by copolymerizing at least one of conjugated dienes or at least one of conjugated dienes and at least one olefin copolymerizable with the conjugated diene. Is done.

The conjugated diene used in the production of 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, ,
5-diethyl-1,3-octadiene, 3-butyl-1,
3-octadiene, chloroprene and the like.

From the viewpoint of obtaining an elastomer which can be developed industrially and has excellent physical properties, 1,3-butadiene and isoprene are particularly preferred, and elastomers such as polybutadiene, polyisoprene and butadiene / isoprene copolymer can be used in the present invention. Is particularly preferred. In this polymer, the microstructure of the polymers is not particularly limited, and any polymer can be suitably used as an object to be hydrogenated.

On the other hand, the method of the present invention is particularly suitably 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 used in the production of the copolymer include the conjugated dienes described above. Examples of the olefin include all monomers copolymerizable with the conjugated diene, and a vinyl-substituted aromatic hydrocarbon is particularly preferable.

In order to obtain an industrially useful and valuable elastomer or thermoplastic elastomer, a copolymer of a conjugated diene and a vinyl-substituted aromatic hydrocarbon is particularly important. Specific examples of the vinyl-substituted aromatic hydrocarbon used for producing the copolymer include styrene, t-butylstyrene, α-methylstyrene, p-methylstyrene, divinylbenzene, 1,1-diphenylethylene, N, N-
Dimethyl-p-aminoethylstyrene, N, N-diethyl-p-aminoethylstyrene, vinylpyridine and the like can be mentioned. Of these, styrene and α-methylstyrene are particularly preferred. 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 a hydrogenated copolymer having high industrial value.

In this copolymer, the monomers include random copolymers, decreasing block copolymers, complete block copolymers, and graft copolymers that are statistically distributed throughout the polymers. In order to obtain an industrially useful thermoplastic elastomer, the content of the vinyl-substituted aromatic hydrocarbon is preferably from 5 to 95% by weight. The vinyl bond of the conjugated diene unit is one of the total conjugated diene units.
0% by weight or more is excellent in polymer performance after hydrogenation, and thus is preferable.

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 type which is coupled with a coupling agent in addition to a linear type. Type, radial type or star type block polymers.

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, tolylene diisocyanate and the like.

Further, a polyepoxy compound can be used as a coupling agent. When this compound is used as a coupling agent, it can be used as a component of the catalyst (b) of the present invention, including components used for coupling. Therefore, it is possible to carry out the hydrogenation reaction economically and efficiently, which is industrially extremely useful.

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

Polymers produced by any other known polymerization methods such as anionic polymerization, cationic polymerization, coordination polymerization, radical polymerization or solution polymerization, and emulsion polymerization 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 olefinically unsaturated bond used in the present invention.

Specific examples of the monomer constituting the polymer include cyclobutene, cyclopentene, cyclooctene, 1,5-cyclooctadiene, 1,5,9-cyclododecatriene, norbornene, and 5-methyl-norbornene. Cycloalkene such as 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-
Norbornene-2-yl acetate, 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 diamide, 5-norbornene-2,3-dicarboxylic anhydride (hymic anhydride), 2,3-dimethyl-5-norbornene-2,3-
Dicarboxylic imide, N-phenyl-2-methyl-5-
Norbornene-2,3-dicarboxylic 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.
1.] Norbornene derivatives such as 2-heptene can be used.

The catalyst of the present invention formed from the bis (cyclopentadienyl) transition metal compound of component (a), the polar compound of component (b) and the organolithium compound of component (c) described above, a) to (c) components and (d)
Each of the catalysts of the present invention formed from the reducing organic compound as a component has good reproducibility and high hydrogenation activity.
These catalyst components can be mixed in advance and then supplied to the reactor or separately supplied in an arbitrary order to carry out the hydrogenation reaction.

According to one preferred embodiment, a revinked polymer having a terminal lithium and containing an olefinically unsaturated bond (this living polymer is a polymer which is hydrogenated simultaneously with component (c)) After the component (b) is added to and reacted, the component (a) or (a)
A catalyst can be prepared by adding a reactant obtained by previously mixing and reacting the component and the component (d). Thereafter, the hydrogenation reaction proceeds by the supply of hydrogen gas.

According to another preferred embodiment, a reaction product obtained by previously reacting the component (b) and the component (c) is added to a solution in which a polymer containing an olefinically unsaturated bond is dissolved, and then separately added. The component (a) or a reactant obtained by previously mixing and reacting the component (a) and the component (d) is added to the solution to prepare a catalyst, and then a hydrogenation reaction can be performed by supplying hydrogen gas. .

When the respective components are mixed in advance, it is desirable to carry out the mixing in an inert atmosphere. Here, the inert atmosphere means an atmosphere that does not react with any participant of a hydrogenation reaction such as nitrogen, helium, neon, or argon. Air and oxygen are not preferred because they oxidize the catalyst and cause deactivation of the catalyst. When the catalyst is preliminarily mixed, the mixing can be performed in a hydrogen atmosphere in addition to the inert atmosphere.

The hydrogenation reaction of the present invention is carried out in a state where the olefinically unsaturated polymer is dissolved in a hydrocarbon solvent, or after the olefinically unsaturated polymer is produced by polymerization in a hydrocarbon solvent, Subsequent hydrogenation can also be carried out. Here, examples of the hydrocarbon solvent include aliphatic hydrocarbons such as pentane, hexane, heptane, and octane; aliphatic hydrocarbons such as cyclopentane, methylcyclopentane, and cyclohexane; and 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 a range of 20% by weight or less.

The concentration of the polymer at the time of performing the hydrogenation reaction of the present invention is not particularly limited.
%, Preferably from 3 to 20% by weight. In the hydrogenation reaction, the above-mentioned catalyst for hydrogenation is added in an atmosphere of an inert gas such as nitrogen or argon or hydrogen, and then hydrogen is supplied under pressure at a pressure of 1 to 100 kg / cm ² , and the polymer solution is further added. Is maintained at a predetermined temperature, and is carried out with or without stirring.

The pressure of hydrogen used in the hydrogenation reaction is as follows:
Preferably it is 1-100 kg / cm < ² > G, more preferably 4-20 kg / cm < ² > G. The temperature range suitable for the hydrogenation reaction is 0 to 150 ° C. Furthermore, preferably 20 to 140 ° C, particularly preferably 70 to 130 ° C
It is. According to the present invention, a hydrogenation reaction can be stably performed at a relatively high temperature under mild conditions where gelation or decomposition of the polymer does not occur, and the reaction rate is high and a high yield can be obtained.

The hydrogenation reaction time of the present invention is 1 minute to 10 minutes.
The reaction time is shorter as the amount of the hydrogenation catalyst is larger and the hydrogen pressure is higher. The hydrogenation reaction of the present invention can be carried out by any of a batch method and a continuous method.

By the hydrogenation reaction of the present invention, a polymer in which 80% or more, preferably 90% or more of the olefinically unsaturated double bond is hydrogenated is obtained. However, the hydrogenation of the aromatic nucleus double bond, if present, is less than 5% and is substantially not hydrogenated. In addition, in the hydrogenation reaction of the present invention, the polymer hardly causes molecular breakage.

According to the method of the present invention, any ratio of unsaturated double bonds in the polymer can be hydrogenated. Further, the hydrogenation catalyst of the present invention can be used for hydrogenating olefins such as styrene.

The polymer hydrogenated by the method of the present invention is prepared by removing catalyst residues from the polymer solution, adding an antioxidant, if necessary, and introducing the polymer solution into hot water together with steam. A method of recovering the solvent by steam distillation and recovering the polymer in the form of a crumb, a method of flowing the polymer solution on a heating roll and evaporating the solvent to recover the polymer, or a method of recovering the polymer by alcohol, acetone The polymer can be isolated from the polymer solution by, for example, a method in which the polymer is poured into a polar solvent, and the polymer is precipitated and recovered.

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

[0066]

EXAMPLES The present invention will now be described more specifically with reference to examples, but the present invention is not limited thereto. The vinyl bond content of the conjugated diene-based polymer in the examples was determined by the Hampton method [R.R.Hampton, Anal.
9, 923 (1949)].

Example 1 In a 10 l autoclave, 5 kg of degassed and dehydrated cyclohexane, 300 g of styrene and 1,3-butadiene 7
Then, 15 g of tetrahydrofuran and 1.1 g of n-butyllithium were added, and the polymerization temperature was 50 ° C.
From the temperature. After the conversion reached almost 100%, the amount of living Li was measured and found to be 13.9 mmol. In this system, 0.63 of γ-butyrolactone was added.
g was added and stirred for 30 minutes. From the change in the color of the polymer solution, it was confirmed that there was no living lithium terminal lithium as a living anion. The polymer obtained at this time had a number average molecular weight of 96,000. However, 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.

Next, a mixture of 0.36 g of bis (cyclopentadienyl) titanium dichloride and 1.31 g of diethylaluminum chloride dissolved in 10 ml of toluene in a nitrogen atmosphere was charged and stirred. At a pressure of 9.0 kg / cm ² G,
The reaction was performed at 80 ° C. for 3 hours. The hydrogenation rate of the obtained hydrogenated polymer was 99%, and the 1,2-vinyl bond content of the polymer before hydrogenation was 40%.

Example 2 After 5 kg of degassed and dehydrated cyclohexane and 1 kg of 1,3-butadiene were charged into a 10-liter autoclave, 15 g of tetrahydrofuran and 0.55 g of n-butyllithium were added, and the polymerization temperature was raised from 50 ° C. Warm polymerization was performed. Living L after conversion reaches almost 100%
The measured amount of i was 5.3 mmol. Next, 95 mg of water was added, and the mixture was stirred for 10 minutes. From the change in the color of the polymer solution, it was confirmed that there was no living lithium terminal lithium as a living anion. Although the number average molecular weight of the polymer obtained at this time was 290,000, 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.

Next, 0.86 g of γ-butyrolactone dissolved in 20 ml of cyclohexane and 1.86 g of n-butyllithium were dissolved.
A reaction product obtained by reacting 23 g in advance under a nitrogen atmosphere for 20 minutes was charged, and 0.52 g of bis (cyclopentadienyl) titanium dichloride and 1.51 g of diethylaluminum chloride dissolved in 10 ml of toluene were further charged under a nitrogen atmosphere. The components mixed in advance were charged in an autoclave and stirred. Thereafter, hydrogen gas was supplied at a pressure of 9.0 kg / cm ² G, and the reaction was carried out at 80 ° C. for 4 hours. The hydrogenation rate of the obtained hydrogenated polymer is 98%,
The 1,2-vinyl bond content of the polymer before hydrogenation was 39%.

Example 3 Polymerization and hydrogenation were carried out in the same manner as in Example 2 except that 0.77 g of γ-butyrolactone was used. The hydrogenation rate of the obtained hydrogenated polymer was 94%.

Example 4 In Example 2, ε was used instead of 0.86 g of γ-butyrolactone.
Polymerization and hydrogenation were carried out in the same manner except that 0.66 g of caprolactone was used. The degree of hydrogenation of the obtained hydrogenated polymer was 59%.

Example 5 A 10-liter autoclave was charged with 5 kg of degassed and dehydrated cyclohexane and 1 kg of 1,3-butadiene, followed by 15 g of tetrahydrofuran and 1.75 g of n-butyllithium.
1 g was added, and the temperature was raised from 50 ° C.
After the conversion reached almost 100%, the amount of living Li was measured and found to be 13.2 mmol. In this system, ε
0.75 g of caprolactone was added and stirred for 30 minutes. From the change in the color of the polymer solution, it was confirmed that there was no living lithium terminal lithium as a living anion. The number average molecular weight of the obtained polymer was 10.
Although it was 20,000, 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.

Next, 1.25 g of ε-caprolactone and 0.2 g of ε-caprolactone were added.
A reaction product obtained by previously reacting 56 g of n-butyllithium under a nitrogen atmosphere was charged, and 0.52 g of bis (cyclopentadienyl) titanium dichloride was added to the reaction product.
A component obtained by mixing 1.88 g of diethylaluminum chloride dissolved in ml of toluene under a nitrogen atmosphere was charged and stirred. Thereafter, hydrogen gas was supplied at a pressure of 8 kg / cm ² G, and a hydrogenation reaction was performed at 80 ° C. The reaction was completed in 4 hours, and the degree of hydrogenation of the obtained hydrogenated polymer was 93%, and the content of 1,2-vinyl bonds in the polymer before hydrogenation was 41%.

Example 6 In Example 7, instead of 0.86 g of γ-butyrolactone, β
Polymerization and hydrogenation were carried out in the same manner except that 0.76 g of propiolactone was used. The hydrogenation rate of the obtained hydrogenated polymer was 99%.

Example 7 5 kg of cyclohexane, 300 g of styrene and 1,3-butadiene 7
Then, 15 g of tetrahydrofuran and 1.1 g of n-butyllithium were added, and a polymerization temperature of 50 g was added.
Polymerization at a temperature rising from 0 ° C. was performed. After the conversion reached almost 100%, the amount of living Li was measured and found to be 13.8 mmol. 0.59 g of 2-pyrrolidone was added to the system and stirred for 30 minutes. From the change in the color of the polymer solution, it was confirmed that there was no living lithium terminal lithium as a living anion. The number average molecular weight of the polymer obtained at this time was 97,000.
By adding 0 g, 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.

Next, a component obtained by previously mixing 0.36 g of bis (cyclopentadienyl) titanium dichloride and 1.31 g of diethylaluminum chloride dissolved in 10 ml of toluene under a nitrogen atmosphere was charged and stirred. 0.0kg / cm ² G at 80 ℃
For 3 hours. The hydrogenation rate of the obtained hydrogenated polymer was 99%, and the 1,2-vinyl bond content of the polymer before hydrogenation was 39%.

Example 8 A 10-liter autoclave was charged with 5 kg of degassed and dehydrated cyclohexane and 1 kg of 1,3-butadiene, 15 g of tetrahydrofuran and 0.55 g of n-butyllithium were added, and the polymerization temperature was raised from 50 ° C. Warm polymerization was performed. After the conversion reached almost 100%, the amount of living Li was measured and found to be 5.2 mmol. Next, 95 mg of water was added, and the mixture was stirred for 10 minutes. From the change in the color of the polymer solution, it was confirmed that there was no living lithium terminal lithium as a living anion. Although the number average molecular weight of the polymer obtained at this time was 21,000, it was confirmed that the color of styryllithium was not added by further adding 100 g of styrene, and that the molecular weight distribution did not change before and after the addition of styrene.

Next, 0.86 g of 2-pyrrolidone dissolved in 20 ml of cyclohexane and 1.23 of n-butyllithium were dissolved.
g was previously reacted under a nitrogen atmosphere for 20 minutes and charged with bis (cyclopentadienyl).
A component in which 0.52 g of titanium dichloride and 1.51 g of diethylaluminum chloride dissolved in 10 ml of toluene were mixed in advance in a nitrogen atmosphere was charged into an autoclave and stirred. Continue with hydrogen gas for 9.
The mixture was supplied at a pressure of 0 kg / cm ² G and reacted at 80 ° C. for 4 hours. The hydrogenation rate of the obtained hydrogenated polymer was 98%, and the 1,2-vinyl bond content of the polymer before hydrogenation was 41%.

Example 9 Polymerization and hydrogenation were carried out in the same manner as in Example 8, except that 1.03 g of ε-caprolactam was used. The hydrogenation rate of the obtained hydrogenated polymer was 93%.

Example 10 Polymerization and hydrogenation were carried out in the same manner as in Example 8 except that 0.86 g of 2-pyrrolidone was replaced by 0.66 g of ε-caprolactam. The hydrogenation rate of the obtained hydrogenated polymer was 61%.

Example 11 A 10-liter autoclave was charged with 5 kg of degassed and dehydrated cyclohexane and 1 kg of 1,3-butadiene, and then 15 g of tetrahydrofuran and 1.5 g of n-butyllithium.
1 g was added, and the temperature was raised from 50 ° C.
After the conversion reached almost 100%, the amount of living Li was measured and found to be 13.4 mmol. Β in this system
-0.48 g of propiolactam was added and stirred for 30 minutes. From the change in the color of the polymer solution, it was confirmed that there was no living lithium terminal lithium as a living anion. The number average molecular weight of the obtained polymer was 10.
Although it was 100,000, 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.

Next, 0.76 g of β-propiolactam and 0.56 g of n-butyllithium were previously reacted under a nitrogen atmosphere, and 0.52 g of bis (cyclopentadienyl) was further charged. Titanium dichloride and 1
A component obtained by mixing 1.88 g of diethylaluminum chloride dissolved in 0 ml of toluene under a nitrogen atmosphere was charged and stirred. Thereafter, hydrogen gas was supplied at a pressure of 8 kg / cm ² G, and a hydrogenation reaction was performed at 80 ° C. The reaction was completed in 4 hours, and the degree of hydrogenation of the obtained hydrogenated polymer was 94%, and the content of 1,2-vinyl bonds in the polymer before hydrogenation was 39%.

Example 12 Polymerization and hydrogenation were carried out in the same manner as in Example 8 except that 0.76 g of β-propiolactam was used instead of 0.86 g of 2-pyrrolidone. The hydrogenation rate of the obtained hydrogenated polymer was 99%.

Example 13 A 10 l autoclave was charged with 5 kg of degassed and dehydrated cyclohexane and 1 kg of 1,3-butadiene.
15 g of tetrahydrofuran and 1.1 g of n-butyllithium were added, and the polymerization temperature was raised from 50 ° C. After the conversion reaches almost 100%, the living Li
The amount was determined to be 13.4 mmol. 0.24 g of water was added to the autoclave and stirred for 10 minutes. From the change in the color of the polymer solution, it was confirmed that there was no living lithium terminal lithium as a living anion. The number average molecular weight of the obtained polymer was 99,000, and 100 g of styrene was further added.
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. Next, 3.8 g of 1,2-epoxytetradecane and 1.1 g of n
-Butyl lithium was previously reacted under a nitrogen atmosphere, and a mixture of 0.40 g of bis (cyclopentadienyl) titanium dichloride and 1.16 g of diethylaluminum chloride dissolved in 10 ml of toluene was mixed under a nitrogen atmosphere. The prepared components were charged and stirred. afterwards,
Hydrogen gas was supplied at a pressure of 8 kg / cm ² G, and a hydrogenation reaction was performed at 70 ° C. Hydrogen absorption was almost completed in 80 minutes, but the reaction was carried out for 4 hours to complete the reaction. The hydrogenation rate of the obtained hydrogenated polymer was 99%, and that of the polymer before hydrogenation was 1,1.
The 2-vinyl bond content was 39%.

Comparative Example 1 Polymerization and hydrogenation were carried out in the same manner as in Example 13 except that 1,2-epoxytetradecane was not added. The hydrogenation rate of the obtained hydrogenated polymer was 45%.

Example 14 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, and 15 g of tetrahydrofuran and 0.55 g of n-butyllithium were added.
Polymerization at a temperature from 0 ° C. was performed. After the conversion reached almost 100%, the amount of living Li was measured and found to be 5.1 mmol. Next, 92 mg of water was added and the mixture was stirred for 10 minutes. From the change in the color of the polymer solution, it was confirmed that there was no living lithium terminal lithium as a living anion. Although the number average molecular weight of the polymer obtained at this time was 300,000, 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.

Next, 2.92 g of 1,2-epoxytetradecane dissolved in 20 ml of cyclohexane and 0.93 g of n-butyllithium were previously mixed under a nitrogen atmosphere for 20 minutes, and bis (cyclopentadienyl) was further added. ) A mixture of 0.36 g of titanium dichloride and 1.05 g of diethylaluminum chloride dissolved in 10 ml of toluene was charged in an autoclave under a nitrogen atmosphere, and the mixture was stirred. 8 kg of hydrogen gas
/ Cm ² G, and reacted at 70 ° C. for 4 hours. The hydrogenation rate of the obtained hydrogenated polymer was 94%, and the 1,2-vinyl bond content of the polymer before hydrogenation was 37%.
Further, it was confirmed by NMR that hydrogenation of the benzene nucleus did not occur.

Comparative Example 2 After polymerization was carried out in the same manner as in Example 14, n was added without adding water.
0.59 g of butyllithium was added, and 0.36 g of bis (cyclopentadienyl) titanium dichloride was further added.
And a component obtained by previously mixing 1.57 g of diethylaluminum chloride dissolved in 10 ml of toluene under a nitrogen atmosphere was charged into an autoclave, and a hydrogenation reaction was carried out under the same conditions as in Example 2. The hydrogenation rate of the obtained hydrogenated polymer was 50%.

Example 15 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, and 15 g of tetrahydrofuran and 0.55 g of n-butyllithium were added.
Polymerization at a temperature from 0 ° C. was performed. After the conversion reached almost 100%, the amount of living Li was measured and found to be 5.2 mmol. Next, 94 mg of water was added and the mixture was stirred for 10 minutes. From the change in the color of the polymer solution, it was confirmed that there was no living lithium terminal lithium as a living anion. Although the number average molecular weight of the polymer obtained at this time was 300,000, 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.

Next, 1.86 g of 1,2-epoxytetradecane dissolved in 20 ml of cyclohexane and 0.93 g of n-butyllithium were previously mixed under a nitrogen atmosphere for 20 minutes, and bis (cyclopentadienyl) was further added. ) A mixture of 0.36 g of titanium dichloride and 1.05 g of diethylaluminum chloride dissolved in 10 ml of toluene was charged in an autoclave under a nitrogen atmosphere, and the mixture was stirred. 8 kg of hydrogen gas
/ Cm ² G, and reacted at 70 ° C. for 4 hours. The hydrogenation rate of the obtained hydrogenated polymer was 58%, and the content of 1,2-vinyl bonds of the polymer before hydrogenation was 38%.
Further, it was confirmed by NMR that hydrogenation of the benzene nucleus did not occur.

Example 16 A polymerization and hydrogenation reaction were carried out in the same manner as in Example 15 except that 1.86 g of 1,2-epoxytetradecane was changed to 4.94 g. The hydrogenation rate of the obtained hydrogenated polymer was 91%.

Example 17 Example 14 was repeated except that 0.93 g of propylene oxide was used instead of 2.92 g of 1,2-epoxytetradecane.
The assembly and hydrogenation reaction were carried out in the same manner as described above. The hydrogenation rate of the obtained hydrogenated polymer was 99%.

[0094]

The hydrogenation catalyst of the present invention has a low degree of activity reduction due to the presence of impurities in the hydrogenation reaction system, is highly active, and can be treated under mild conditions by the hydrogenation method of the present invention using this catalyst. It is possible to selectively hydrogenate olefinically unsaturated bonds in the polymer chain at a high reaction rate.

Continuation of the front page Examiner Kunihiko Sato (56) References JP-A-3-223305 (JP, A) JP-A 4-248815 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) ) C08F 8/00-8/50

Claims (3)

(57) [Claims] (A) The following formula (1): (Where 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, an allyloxy group A bis (cyclopentadienyl) transition metal compound represented by the formula: (b) a lactone compound, a lactam compound and an epoxy compound, which is an acyloxyl group, a carbonyl ligand, a β-diketone ligand or a halogen atom. And ( c) an organolithium compound, and (b) a lactone ring or lactone of component (b).
When the equivalent ratio of the lithium atom of the tom ring / (c) component is 1 or less
Or epoxy group of component (b) / component of (c)
Olefinic non-olefins having an equivalent ratio of lithium atoms of 2 or less
Hydrogenation catalyst for polymers containing saturated bonds. Wherein upper Symbol (a), is formed from (b) and (c) components and the other, further (d) an aluminum compound, a reducing organometallic compound selected from the group consisting of zinc compounds and magnesium compounds The hydrogenation catalyst according to claim 1. 3. The hydrogenation catalyst according to claim 1 or 2.
In the presence of a polymer containing an olefinically unsaturated bond
Select the olefinically unsaturated bond by contact with hydrogen
Olefinic unsaturation characterized by selective hydrogenation
A method for hydrogenating a polymer containing a sum bond.