JPS62207303A - Hydrogenation of conjugated diene polymer - Google Patents

Abstract

PURPOSE:To obtain a hydrogenated device polymer excellent in weather resistance, heat resistance and oxidation resistance, by hydrogenating a polymer obtained by (co)polymerizing a conjugated diene in the presence of a specified catalyst in an inert organic solvent. CONSTITUTION:A catalyst (B) is obtained by mixing 1mol of a bis(cyclopentadienyl)titanium compound (a) of the formula [wherein R and R' are each a 1-8C alkyl, alkoxy, 6-10C aryl(oxy), cycloalkyl, halogen or the like] with 0.5-15mol of a hydrocarbon compound (b) containing least one metal selected from among Na, K, Rb and Cs (e.g., Na-naphthalene) at -80-50 deg.C in a solution in a H2 gas atmosphere. A polymer formed by (co)polymerizing a conjugated diene (A) [e.g., a copolymer of 1,3-butadiene and/or isoprene with (alpha-methyl)styrene] is hydrogenated at 30-180 deg.C and a H2 pressure of 5-200kg/cm<2> for several min to 50hr in the presence of an inert organic solvent such as tetrahydrofuran in the presence of catalyst B in an amount equivalent to 0.2-50mM of component (a) per 100g of the polymer to obtain a hydrogenated polymer of such a degree of hydrogenation that at least 50% of the unsaturated bonds in the starting polymer are hydrogenated.

Description

Detailed Description of the Invention <Industrial Application Field> The present invention relates to a hydrogenation method for imparting weather resistance, heat resistance, etc. to an olefinically unsaturated double bond gold-containing polymer. This invention relates to a method for preferentially hydrogenating olefinically unsaturated double bonds in polymer chains under mild hydrogenation conditions using a hydrogenation catalyst containing a pentagenyl titanium compound as a main component.

<Prior Art> Olefinically unsaturated double bond gold-containing polymers, typified by conjugated diene polymers, are generally widely used industrially as elastomers and the like. However, while the olefinic unsaturated double bonds in these polymers are advantageously used for vulcanization, etc., they are the cause of deterioration of weather resistance and heat resistance. In particular, block polymers obtained from conjugated dienes and vinyl-substituted aromatic hydrocarbons are used without vulcanization as thermoplastic nidistomers, transparent impact-resistant resins, or as modifiers for various resins. Due to the unsaturated double bond, it has insufficient weather resistance, oxidation resistance, ozone resistance, heat resistance, etc., and has the disadvantage that its uses are limited.

This disadvantage of poor stability can be significantly improved by hydrogenating the polymer to eliminate unsaturated double bonds in the polymer chain. Many methods have been proposed for hydrogenating olefinically unsaturated double bond gold-containing polymers for this purpose, including methods using supported heterogeneous catalysts and methods using homogeneous organometallic complex catalysts. Homogeneous catalysts are generally used industrially as polymer hydrogenation catalysts because they have higher activity and only require a small amount of use.

<Problems to be solved by the invention> However, the so-called Ziegler-type homogeneous catalyst is generally unstable and has difficulty in reproducibility, and requires water deashing of the olefinic unsaturated double bond in the aromatic nucleus. However, there are disadvantages such as the complexity of the process. Therefore, in order to carry out hydrogenation economically, it is strongly desired to develop a catalyst that does not require deashing, that is, a highly active catalyst that has a small amount of catalyst adsorption that has little effect on the stability of the polymer, and that can perform hydrogenation with a small amount of use. The current situation is that

Means and Action for Solving the Problems> The present inventors have developed a catalyst consisting of a bis(cyclopentagenyl) titanium compound and a lithium 71 compound as a polymer hydrogenation catalyst that has significantly improved the above drawbacks. (Special application 1986-6
No. 178, Japanese Patent Application No. 58-186983) and a catalyst consisting of a bis(cyclopentadienyl) titanium compound and a compound containing aluminum, zinc, and magnesium (
Patent Application No. 59-147589) was first proposed, but as a result of further intensive study, we found that not only lithium compounds, but also bis(cyclopentagenyl)titanium compounds, sodium compounds, potassium compounds, which have the ability to reduce them, We have discovered that even if rubidium compounds or cesium compounds are combined, if the conditions are selected, they can exhibit extremely high activity with good reproducibility even in small amounts and have hydrogenation selectivity for olefinically unsaturated double bonds, and have developed the present invention. It has been completed.

That is, the present invention provides a method for preparing an olefinically unsaturated double bond gold-containing polymer in an inert organic solvent (4) at least one bis(cyclopentagenyl) titanium compound represented by the following general formula (provided that Medium R
, R' is a c1 to c8 alkyl group or alkoxy group,
A group selected from a C6 to CtO 7-aryl group, an aryloxy group, a cycloalkyl group, a halogen group, and a carzenyl group, and R and R' may be the same or different. ) and) at least one sodium atom, potassium atom,
At least one hydrocarbon compound having a rubidium atom or a cesium atom, and hydrogenating the unsaturated double bonds of the conjugated diene units in the polymer by contacting with hydrogen in the presence of a catalyst comprising: The present invention relates to a method for hydrogenating a polymer.

The term olefinically unsaturated double bond-containing polymer used in the present invention has an olefinically unsaturated carbon-carbon double bond in the polymer chain or in the side chain. All jf rimmers are included. Preferred representative examples include conjugated diene polymers and random, block, and graft copolymers of conjugated dienes and olefin monomers.

Such conjugated diene polymers include copolymers obtained by copolymerizing a conjugated diene homoprimer and a conjugated diene, or at least i@ of a conjugated diene and at least one olefin monomer copolymerizable with a conjugated diene. . Conjugated dienes used in the preparation of such conjugated diene polymers generally include conjugated dienes having from 4 to about 12 carbon atoms, specific examples include 1,3-butadiene, inoprene, 2゜3-
Dimethyl-1,3-butadiene, 1,3-penta, citric acid, 2-methyl-1,3-pentadiene, 1°3-hexadiene, 4,5-diethyl-1,3-octadiene,
Examples include 3-butyl-1,3-octadiene and chloroprene. From the viewpoint of obtaining an elastomer that can be industrially advantageously developed and has excellent physical properties, 1,3-butadiene and isoprene are particularly preferred, and elastomers such as boribbutadiene, I-liisoprene, and butadiene/isoprene copolymers are suitable for the practice of the present invention. Particularly preferred. In such a polymer, the microstructure of the polymer chain is not particularly limited and any structure can be suitably used; however, if there are too few 1,2-vinyl bonds, the solubility of the polymer after hydrogenation will decrease, making it difficult to hydrogenate uniformly. Since solvents are limited for this purpose, polymers containing about 30% or more of such bonds are more preferred.

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 monomer copolymerizable with the conjugated diene. Suitable conjugated dienes used in the preparation of such copolymers include the conjugated dienes described above, while olefin monomers include all monomers copolymerizable with conjugated dienes, but especially vinyl-substituted aromatic hydrocarbons. is preferred. That is, in order to fully exhibit the effect of the present invention, which selectively hydrogenates only the unsaturated double bonds of the conjugated diene unit, and to obtain industrially useful and valuable Nistomers and thermoplastic elastomers, it is necessary to combine the conjugated diene and Of particular interest are colimers with vinyl-substituted aromatic hydrocarbons. Specific examples of vinyl-substituted aromatic hydrocarbons used in the preparation of such copolymers include styrene, t-butylstyrene, α-methylstyrene, p-methylstyrene, kuhinylbenzene, 1,1-diphenylethylene, N,N- dimethyl-p-aminoethylstyrene, N,
Examples include N-diethyl-p-amineethylstyrene, and styrene and α-methylstyrene are particularly preferred. As specific examples of copolymers, butadiene/styrene copolymers, isoprene/styrene copolymers, butadiene/α-methylstyrene copolymers, etc. are most preferred since they provide hydrogenated copolymers of high industrial value.

Such copolymers include random copolymers, tapering block copolymers, complete block copolymers, and graft copolymers in which the monomers are statistically distributed throughout a 4-limer chain.

In order to obtain an industrially useful thermoplastic nidistomer,
Vinyl-substituted aromatic hydrocarbon content is 5% to 95% by weight
A weight of 2 is preferred, and a clock co-remer is more preferred. In addition, the 1,2-vinyl bond in the conjugated diene unit, which accounts for 20% to 70% by weight of the entire conjugated diene unit, has excellent 2-remer performance after hydrogenation, has a low solution viscosity, and is highly effective for uniformly carrying out the hydrogenation reaction. It is preferable.

Such a block copolymer comprises at least one polymer block B mainly consisting of a vinyl-substituted aromatic hydrocarbon and at least one polymer block B mainly consisting of a conjugated diene.
The block B may contain a small amount of a conjugated diene and the block B may contain a small amount of a vinyl-substituted aromatic hydrocarbon. Such block copolymers include not only linear type block copolymers but also so-called branched type, radial type, and star type block copolymers coupled with a coupling agent.

Furthermore, in the method of the present invention, unsaturated double bond-containing polymers such as polynordarene and polyglycidyl acrylate are also applicable.

The polymer used in the hydrogenation reaction of the present invention generally has a molecular weight of about 1,000 to about 1,000,000, and can be carried out by any known polymerization method, such as anionic polymerization, cationic polymerization, coordination polymerization, or radical polymerization. , or solution polymerization method,
Polymers produced by emul/kyon polymerization method or the like can be used.

The catalyst in the polymer hydrogenation method of the present invention is C1~
R and R' may be a group selected from a C8 alkyl group or alkoxy group, a C6 to CtO aryl group, an arylox group, a cycloalkyl group, a halogen group, and a carzenyl group, and R and R' may be the same or different. ) at least one bis(cyclopentagenyl) titanium compound represented by [F]) at least one sodium atom,
It is a combination of at least one kind of hydrocarbon compound having a potassium atom, a rubidium atom, or a cesium atom.

Specific examples of such catalysts include bis(cyclopentagenyl)titanium dimethyl, bis(cyclopentagenyl)titanium diethyl, bis(cyclopentagenyl)titanium di-n-butyl, and bis(cyclopentagenyl)titanium di-n-butyl. ) titanium) -5ec-butyl, bis(cyclopentagenyl) titanium dihexyl, bis(cyclopentagenyl) titanium dioctyl, bis(cyclopentagenyl) titanium jetoxide, bis(cyclopentagenyl) titanium jetoxide, Screw(
cyclopentagenyl) titanium jetoxide, his(cyclopentagenyl) titanium diphenyl, bis(cyclopentagenyl) titanium di-m-)lyl,
Bis(cyclopentagenyl)titanium-)-p-tyl, bis(cyclopentadienyl)titanium di-m, p-xylyl, bis(cyclopentagenyl)titanium di-4-ethylphenyl, bis(cyclopentagenyl)titanium di-4-ethylphenyl, titanium-)-4-i tylphenyl, bis(
cyclopentagenyl) titanium di-4-hexylphenyl, bis(cyclopentagenyl) titanium diphenoxy P1 bis(cyclopentagenyl) titanium dichloride P1 bis(cyclopentagenyl) titanium dichloride P1 bis(cyclopentagenyl) titanium dichloride P1 dicarzenyl) titanium dichloride, bis(cyclopentagenyl) titanium dichloride P1 his(cyclopentagenyl) fl'nium dicarzenyl, bis(cyclopentagenyl) titanium chloride P methyl, bis(cyclopentagenyl) Examples include titanium chloride P ethoxide, bis(cyclopentadienyl) titanium chloride phenoxy P, and the like, which can be used alone or in combination with each other.

Among these bis(cyclopentagenyl) titanium compounds, preferred are those that have high hydrogenation activity toward olefinically unsaturated double bonds in the polymer and can selectively hydrogenate unsaturated double bonds under mild conditions. Examples include bis(cyclopentagenyl) titanium dimethyl, bis(
cyclopentagenyl) titanium di-n-butyl, bis(cyclopenta, phenyl) titanium dichloride, bis(cyclopentagenyl) zirconium cyfuromide, bis(cyclopentagenyl) titanium diphenyl, bis(cyclopentagenyl) titanium jeep
−) Lyle, bis(cyclopentagenyl)titanium
Dicarzenyl is mentioned.

Furthermore, they can be handled stably, and when combined with the reducing metal compound of C3), the activity can be easily expressed in small amounts. cyclopentadienyldiphenyl, bis(cyclopentadienyl)titanium di-p-1lyl, bis(cyclopentadienyl)titanium-)-p-
)! Jru is the most preferred because it has excellent solubility.

On the other hand, as the catalyst, any organic metal compound having a reducing ability can be used, but it is essential to use sodium compounds, potassium compounds, rubidium compounds, and cesium compounds. These may be used alone or in combination with each other. Japanese Patent Application No. 58-6718 and Japanese Patent Application No. 14758, filed earlier by the present inventors
In No. 9, it was essential to use a lithium compound, an aluminum compound, a zinc compound, or a magnesium compound. It is surprising to find that by selecting a bis(cyclopentagenyl) titanium compound, high unsaturated double bond hydrogenation activity can be expressed even when sodium compounds, potassium compounds, rubidium compounds, and cesium compounds are used. That's true.

Specific examples of organometallic compounds having such reducing ability include methyl sodium, ethyl sodium, n-propyl sodium, isozolobyl sodium, n-butyl sodium, 5ec-butyl sodium, t-butyl sodium, and n-pentyl sodium. Sodium, n-hexyl sodium, benzyl sodium, phenyl sodium, triphenylmethyl sodium, cyclopentagenyl sodium, sodium naphthalene, hexynyl sodium, phenylethyl sodium, methyl potassium, ethyl potassium, triphenylmethyl potassium, phenylethyl potassium , ethyl potassium, benzyl rubidium,
Examples include ethyl cesium and benzyl cesium.

Furthermore, if desired, a lithium compound may be used in combination with these organometallic compounds. Lithium compounds used in such combinations include methyllithium,
Examples include ethyllithium, n-propyllithium, n-butyllithium, 5eC-butyllithium, isobutyllithium, n-hexyllithium, phenyllithium, p-1 lyllithium, xylyllithium, and the like.

Among these metal compounds, preferable ones that exhibit high hydrogenation activity include methyl sodium, ethyl sodium, n-propyl sodium, isopropyl sodium, n-butyl sodium, 5ec-butyl sodium,
Examples include t-butyl sodium and sodium naphthalene. In particular, the most preferable system is a combination of bis(cyclopentagene (ru)titanium)-p-)lylu and sodium naphthalene and/or methylsodium. Of course, the present invention is not limited to these.

In the method of the present invention, it is preferable that the metal molar ratio between catalyst (4) and catalyst 03) is 110.5 to 1/15.

If the value of the molar ratio exceeds 110.5, the catalyst (4) will not be sufficiently reduced, and therefore the hydrogenation activity will be insufficient, making it difficult to hydrogenate the polymer under mild conditions. On the other hand, the value of molar ratio is 1/15
If it is less than This is not only undesirable, but also causes gelation of the polymer and side reactions. A suitable molar ratio of catalyst titanium/catalyst metal is 1/1 to 115.
It is. Of course, the molar ratio is appropriately selected and carried out depending on the type and combination of catalysts (4) and catalysts (4) and hydrogenation conditions to be selected.

A preferred embodiment of the hydrogenation reaction of the present invention is carried out in a solution of the olefinically unsaturated double bond gold-containing polymer dissolved in an inert organic solvent. "Inert organic solvent" means a solvent that does not react with any participant in the hydrogenation reaction. Suitable solvents include, for example, aliphatic hydrocarbons such as n-pentane, n-hexane, n-hebutane, and n-octane, alicyclic hydrocarbons such as cyclohexane and cycloheptane, diethyl ether, and tetrahydropolymer. Ethers such as lofuran may be used alone or in mixtures. Thus, aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene can also be used as long as the aromatic double bonds are not hydrogenated under the selected hydrogenation reaction conditions.

More preferably, the hydrogenation polymer used in the present invention is
It is advantageous to carry out the polymerization in the same solvent as that used in the hydrogenation reaction and to use the polymerization solution as it is in the hydrogenation reaction.

The hydrogenation reaction of the present invention is carried out in a solution in which the polymer is dissolved at a concentration of 1 to 50% by weight, preferably 3 to 25% by weight, based on the solution.

In the hydrogenation reaction of the present invention, the polymer solution is generally maintained at a predetermined temperature, a hydrogenation catalyst is added with or without stirring, and then hydrogen gas is introduced to increase the pressure to a predetermined pressure. It is carried out by

On the other hand, it is preferable to use a catalyst that has been reduced by mixing catalyst (1) and catalyst (2) in advance. In particular, in the present invention, the catalyst (1) and the catalyst (2) are mixed in a solution under a hydrogen gas atmosphere at -8
It is preferable to use a mixture at 0 to 50°C because it has the highest activity. Of course, the hydrogenation reaction can be carried out either by adding either catalyst (4) or catalyst Q3) to the polymer solution separately or at the same time. Moreover, each catalyst may be added to the polymer solution as it is, or may be added as a solution in an inert organic solvent. As the inert organic solvent used when each catalyst is used as a solution, the above-mentioned various solvents that do not react with any of the participants in the hydrogenation reaction can be used. Preferably, it is the same solvent as used in the hydrogenation reaction.

Additionally, each catalyst needs to be handled under an inert atmosphere. Inert atmospheres include, for example, helium, neon,
This means an atmosphere that does not react with any participating bodies in the hydrogenation reaction, such as argon. Air and oxygen are not preferred because they oxidize the catalyst and cause deactivation of the catalyst.

When the catalysts (1) and 2) are mixed in advance or when the catalysts are added to the hydrogenation reactor, it is most suitable to carry out the reaction under a hydrogen atmosphere.

On the other hand, the preferred amount of catalyst added in the present invention is 0.2 to 50 mmol of catalyst Q per 100 f of polymer.

Within this addition amount range, it is possible to preferentially hydrogenate unsaturated double bonds in the polymer, and hydrogenation of aromatic double bonds does not substantially occur, resulting in extremely high hydrogenation selectivity. Realized. Although the hydrogenation reaction is possible even when the amount exceeds 50 mmol, using more catalyst than necessary is disadvantageous, such as being uneconomical and complicating deashing and removal of the catalyst after the hydrogenation reaction. The preferred amount of catalyst added to quantitatively hydrogenate the unsaturated double bonds in the polymer under selected conditions is the catalyst component (4
) is 0.5 to 25 mmol per 100 ml of polymer.

The hydrogenation reaction of the present invention is carried out using elemental hydrogen, preferably introduced into the polymer solution in gaseous form. More preferably, the hydrogenation reaction is carried out under stirring, so that the introduced hydrogen can be brought into contact with the polymer quickly enough. The hydrogenation reaction is generally carried out at a temperature range of 30 to 180°C. If it is below 30°C, the activity of the catalyst will decrease and the hydrogenation rate will also be slow, requiring a large amount of catalyst, which is not economical.
If the temperature exceeds 80° C., decomposition and gelation of the polymer are likely to occur, and hydrogenation of the aromatic nucleus portion is also likely to occur, resulting in a decrease in hydrogenation selectivity, which is not preferable. More preferably, the temperature is in the range of 50 to 100°C.

The pressure of hydrogen used in the hydrogenation reaction is 5 to 200 storage/sub2
is suitable. If the hydrogenation rate is less than 2#/-, the hydrogenation rate will slow down and practically reach a plateau, making it difficult to increase the hydrogen rate.If it exceeds 200#/cWt2, the hydrogenation reaction will be completed at the same time as the pressure is increased, making it virtually meaningless. This is not preferable because it causes unnecessary side reactions and gelation. A more preferable hydrogenation pressure is 10 to 60 Ail/cm'', but the optimum hydrogen pressure is selected in correlation with the amount of catalyst added, etc., and substantially the hydrogen pressure becomes higher as the preferable amount of catalyst becomes smaller. It is preferable to select one side and implement it.

The hydrogenation reaction time of the present invention is usually several minutes to 50 hours. The hydrogenation reaction time is appropriately selected within the above range by selecting other hydrogenation reaction conditions.

The hydrogenation reaction of the present invention may be carried out by any method such as a double method or a continuous method. The progress of the hydrogenation reaction can be monitored by tracking the amount of hydrogen absorbed.

By the method of the present invention, it is possible to obtain a hydrogenated polymer in which 50% or more, preferably 90% or more of unsaturated double bonds in the bilimer are hydrogenated. Furthermore, when a copolymer of a conjugated diene and a vinyl-substituted aromatic hydrocarbon is hydrogenated, the hydrogenation rate of the unsaturated double bond in the conjugated diene unit is 50% or more, preferably 90% or more, and A selectively hydrogenated hydrogenated polymer with an addition rate of 10% or less can be obtained.

The 4-limer hydrogenation catalyst according to the present invention has extremely excellent selectivity,
Since the aromatic nucleus portion is not substantially hydrogenated, it is extremely advantageous industrially.

Catalyst residues can be removed from a polymer solution subjected to a hydrogenation reaction by the method of the present invention, and the hydrogenated polymer can be easily isolated from the solution. For example, the polymer is precipitated by adding a polar solvent such as acetone or alcohol, which is a poor solvent for the hydrogenated polymer, to the reaction solution after hydrogenation, or the reaction solution is poured into boiling water with stirring and then distilled together with the solvent. This can be carried out by a method in which the solvent is removed by removing the solvent. In the process of isolating these hydrogenated polymers, most of the catalyst is also decomposed and removed, and is removed from the polymer. Therefore, no special operation is required to deash or remove the catalyst, but if you want to remove the catalyst more effectively, it is recommended to add an acidic polar solvent or water to the 2 Lima monohydrogenation reaction solution. preferable.

As described above, according to the present invention, it is possible to hydrogenate an olefinically unsaturated double-bonded gold polymer under mild conditions using a highly active catalyst, especially in a polymer of a conjugated diene and a vinyl-substituted aromatic hydrocarbon. It has now become possible to hydrogenate the unsaturated double bonds of the conjugated diene units extremely selectively.

The hydrogenated polymer obtained by the method of the present invention can be used as an elastomer, thermoplastic nidistomer, or thermoplastic resin with excellent weather resistance and oxidation resistance, and may be added with additives such as ultraviolet absorbers, oils, fillers, etc. It is used in combination with other elastomers and resins, and is extremely useful industrially.

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

In addition, the block content in the vinyl-substituted aromatic hydrocarbon block polymer in the examples is M.

Kolthoffis, J., Polymer Sc.
i, Vol. 1, p. 429 (1946).
, R. Hampton, Anal.

Ohem, Vol. 29, p. 923 (1949)).

Examples 1 to 6 After extracting and washing each 1 limer shown in Table 1 with acetone, it was dissolved in purified and dried cyclohexane, and 2 limers were dissolved in cyclohexane at a concentration of 15%.
Adjusted to.

1,000 t of this polymer solution was charged into a sufficiently dried 32 autoclave equipped with a stirrer, and after purging the system with hydrogen, the temperature was maintained at 60'C with stirring.

then bis(cyclopentadienyl)titanium) −
A tetrahydro-7 run solution containing 2 mmol of p-tolyl and a tetrahydro-7 run solution containing 6.0 mmol of sodium naphthalene 100FI! A' and total room temperature, 2.0kf
/α2 catalyst solution (T t /Na
The entire amount (molar ratio = 173) was immediately charged into an autoclave, and dried gaseous hydrogen was supplied at a pressure of 2014/cm'' to conduct a hydrogenation reaction for 3 hours with stirring.

Return the reaction solution to room temperature and pressure and remove it from the autoclave.
The 2-limer was precipitated by adding it to a large amount of methanol, and the mixture was filtered and dried to obtain a white hydrogenated polymer.

The hydrogenation rate of the obtained hydrogenated polymer was determined by infrared absorption spectrum and is shown in Table IK.

Table 1 (Note 1) A: Tuffprene A (manufactured by Asahi Kasei Kogyo)...Styrene/butadiene linear block polymer B: Solbrene T 411 (Japanese Nidistomer family)
Styrene/butadiene block polymer C: Kraton D-1101 (made by Shell) Styrene-butadiene-styrene block polymer D; Kraton D-txxx (made by Shell) Styrene isoprene-styrene block polymer 0 Mar E: Nl8SOPB B-2000 (Nippon Soda)
...Liquid polybutadiene F: 7-Nrex (manufactured by Nippon Zeon) ...Polynorzernene (Note 2) Hydrogenation rate of unsaturated double bonds in the olefin part.

Examples 7 to 12 Tafsolen (Asahi Kasei Corporation) prepared according to Example 1
1000 f of a 15% cyclohexane solution (manufactured by Co., Ltd.) was charged into a sufficiently dried 3° C. autoflave equipped with a stirrer, the inside of the system was purged with hydrogen, and the temperature was maintained at 70° C. with stirring.

Next, bis(cyclopentagenyl) titanium
-) 20 cyclohexane solution containing 3.0 mmol of
0- and the metal compounds shown in Table 2 as (of the catalyst) 6.0
A cyclohexane solution containing 100 mmol of
The entire catalyst solution (Ti/metal ratio molar ratio = 1/2) mixed under a hydrogen pressure of 0Jrf/an'' was immediately charged into an autoclave, and dried gaseous hydrogen was added at 20Jcf.
/cm2 and the reaction was carried out for 4 hours.

After the reaction, the same treatment as in Example 1 was carried out to obtain a hydrogenated polymer. The results are shown in Table 2.

The following margins are Examples 13 to 19 Tuffrene prepared according to Example 1 (Asahi Kasei Co., Ltd.)
3,000 f of a 15% cyclohexane solution (manufactured by Co., Ltd.) was charged into a sufficiently dried 5 L autoclave equipped with a stirrer, and after replacing the inside of the system with hydrogen, the autoclave was maintained at 60° C. with stirring.

Next, 200 mmol of a tetrahydroalane solution containing 10.0 mmol of each bis(cyclopentadienyl) titanium compound shown in Table 3 as a catalyst (t) was charged into an autoclave and stirred for 10 minutes. Next, 250 mmol of a tetrahydrofuran solution containing 40 mmol of sodium naphthalene was charged (Ti/Na molar ratio 1/4), and dried hydrogen gas was supplied to 15.0 mm at a pressure of 9/cm'', and the mixture was stirred for 3 hours.
The hydrogenation reaction was carried out for hours. A hydrogenated polymer was obtained by processing in the same manner as in Example 1. The results are shown in Table 3.

Examples 20 to 22 Below are blank spaces Examples 20 to 22 In the same manner as in Example 13, a polymer hydrogenation reaction was carried out using the catalyst shown in Table 4. Catalyst (2) used 4 mmol per 100 polymer, and catalyst (2) was prepared at the metal molar ratio shown in Table 4.
Hydrogenation reaction was carried out at 70°C for 4 hours. The results are shown in Table 4.

Margin below

Claims (1)

[Claims] 1. A polymer obtained by polymerizing or copolymerizing a conjugated diene is prepared by (A) bis(cyclo At least one type of (pentadienyl) titaeum compound (wherein R and R' are C_1 to C_8
alkyl group or alkoxy group, C_6 to C_1_0
is a group selected from an aryl group, an aryloxy group, a cycloalkyl group, a halogen group, and a carbonyl group, and R and B' may be the same or different. ) and (B) at least one type of hydrocarbon compound having at least one sodium atom, potassium atom, rubidium atom or cesium atom, by contacting with hydrogen in the presence of a catalyst consisting of a conjugated diene unit in the polymer. Polymer hydrogenation method 2, characterized in that R and R' are groups selected from chloro, bromo, phenyl, and p-tolyl groups, and (B) is sodium Method 3 according to claim 1, in which the polymer is naphthalene, and method 3 according to claim 1, in which the polymer is a copolymer of 1,3-butadiene and/or isoprene with styrene and/or α-methylstyrene.