JPS6147706A - Hydrogenation of living polymer - Google Patents

Abstract

PURPOSE:To produce a hydrogenated polymer having excellent weather resistance, heat resistance and oxidation resistance, by polymerizing a conjugated eiene, etc., using an organic Li compound as a catalyst, and hydrogenating the obtained living polymer using titanocene diaryl compound and an organic Li compound as the catalyst. CONSTITUTION:A conjugated diene is polymerized or copolymerized with a monomer copolymerizable with conjugated diene, using an organic lithium compound as the polymerization catalyst to obtain a living polymer. The polymer is made to contact with H in the presence of a catalyst composed of (A) one or more titanocene diaryl compounds of formula (R1-R6 are H or 1-4C alkyl hydrocarbon group; at least one of R1-R3 and R4-R6 is H) and (B) one or more alkyl lithium compounds of formula R-Li (R is 1-6C alkyl) to effect the selective hydrogenation of the unsaturated double bond of the conjugated diene unit in the living polymer.

Description

[Detailed Description of the Invention] [Prior Art] In polymers obtained by polymerizing or copolymerizing conjugated dienes, unsaturated double bonds are advantageously used for vulcanization, etc., but such double bonds have poor weather resistance. However, it has the disadvantage of poor stability such as heat resistance and oxidation resistance. These drawbacks are significantly improved by hydrogenating the polymer. However, when hydrogenating a polymer, it is difficult to hydrogenate due to the effects of the viscosity of the reaction system, steric hindrance of the polymer, etc., and a large amount of catalyst is required and the hydrogenation reaction needs to be carried out at high temperature and high pressure. Furthermore, after completing the hydrogenation,
There are drawbacks such as the fact that it is extremely difficult to physically remove the catalyst and it is virtually impossible to separate it completely. Therefore, in order to economically hydrogenate polymers, it is necessary to use a polymer in a low amount that does not require deashing, and to have high activity that can selectively hydrogenate olefinically unsaturated double bonds under mild conditions. At present, there is a strong desire for the development of hydrogenation catalysts.

[Problems to be solved by the present invention]

The present invention has discovered a highly active hydrogenation catalyst that can selectively hydrogenate olefinically unsaturated double bonds in polymers obtained by polymerizing or copolymerizing conjugated dienes under mild conditions and in small amounts. However, the problem to be solved this summer is to find a method to obtain hydrogenated polymers with excellent stability such as weather resistance, heat resistance, and oxidation resistance.

[Means and effects for solving the problems] The present invention provides a hydrogenation catalyst comprising a titanocene diaryl compound and an alkyl lithium for the hydrogenation of an olefinically unsaturated group-containing living polymer obtained by using an alkyl lithium as a polymerization catalyst. When used, it exhibits extremely high hydrogenation activity and can selectively hydrogenate the unsaturated double bonds in the living polymer under mild conditions and in an amount used that does not require deashing. It is based on an amazing fact.

That is, the present invention provides a method for hydrogenating a living polymer in an inert organic solvent, in which (4) a conjugated diene is polymerized using an organolithium as a polymerization catalyst, or a conjugated diene and a monomer copolymerizable with the conjugated diene are copolymerized. (1) At least one type of titanocene diaryl compound R1 shown in (a) below (wherein R1-R6 represents hydrogen or an alkyl hydrocarbon group having 1 to 4 carbon atoms, and R1-R8 and one or more of R4-R6 is hydrogen.) and (c) alkyl lithium represented by the general formula R-Li (wherein R represents an alkyl group having 1 to 6 carbon atoms) A slipping polymer characterized by selectively hydrogenating unsaturated double bonds of conjugated diene units in the living polymer by contacting with hydrogen in the presence of a hydrogenation catalyst containing a small amount of a compound (or at least one kind of compound). This invention relates to a catalytic hydrogenation method.

It is already known that the titanocene diaryl compound as shown by the general formula (a) according to the present invention can be stably handled in air at room temperature and is easily isolated (for example, L, Su
mmers et al., J. Am, Cbem, Soc.
Vol. 77, p.-3604 (1955), M. D.
Rausch et al., J. Organometal, ]-
Chem, Vol. 10, p. 127 (1967), etc.).

In addition, the present inventors have discovered that such titanocene diaryl compounds alone have high hydrogenation activity, and have already filed a patent application (Japanese Patent Application No. 76,614/1989). As a result of extensive research into a method for efficiently and economically hydrogenating living polymers containing olefinically unsaturated groups using this earlier application's olefin hydrogenation catalyst system, the present inventors discovered that titanocene diaryl compounds and alkyl lithium compounds The present inventors have discovered that, under certain conditions, a hydrogenation catalyst exhibits even higher hydrogenation activity than the use of a titanocene diaryl compound alone, leading to the completion of the present invention.

The olefinically unsaturated double bond hydrogenation catalyst component ω) according to the present invention is represented by the general formula (a) R1°6. However, R1-R6 are hydrogen or carbon number 1
-4 alkyl hydrocarbon groups, R1-R8 and R
One or more of 4-R6 is hydrogen. Those in which the alkyl carbon group has 5 or more carbon atoms, and R, ~R8 or R4
If -R6 is all an alkyl group, it is difficult to synthesize in good yield due to steric hindrance, and the storage stability at room temperature is also poor, which is not preferred.

Furthermore, it is difficult to synthesize a compound in which the alkyl hydrocarbon group is ortho to titanium. Specific examples of such hydrogenation catalysts include diphenylbis(η-cyclopentadienyl)titanium, di-m-11rubis(η-cyclopentadienyl)titanium, and di-p-)! J Rubis (
η-cyclopentadienyl) titanium, g-m, p-
Examples include xylylbis(η-cyclopentagenyl)titanium, bis(4-ethylphenyl)bis(η-cyclopentagenyl)titanium, bis(4-butylphenyl)bis(η-cyclopentagenyl)titanium, etc. . Compounds with a large number of carbon atoms in the alkyl carbon group have poor storage stability, while good solubility in certain types of organic solvents.
-1! Most preferred is Jrubis(η-cyclopentagenyl)titanium.

On the other hand, as the catalyst component (C), an organometallic compound capable of reducing the titanocene diaryl compound of the catalyst component CB), such as an organolithium compound, an organoaluminum compound, an organozinc compound, an organomagnesium compound, etc., may be used singly or together. Living polymers can be hydrogenated by using them in combination. However, in order to exhibit high activity and selectively hydrogenate the olefinically unsaturated double bonds in the living polymer, it is essential to use an organolithium compound. That is, by using a titanocene diaryl compound in combination with an alkyl lithium compound, the object of the present invention can be suitably achieved, and surprisingly, with the addition of a small amount of catalyst and under mild conditions,
It is possible to hydrogenate olefinically unsaturated double bonds in living polymers almost quantitatively and preferentially.

Such a catalyst component (Q has the general formula R-i, i (
However, R represents an alkyl group having 1 to 6 carbon atoms. )
Alkyllithium compounds represented by are preferably used, and specific examples include methyllithium, ethyllithium, n-propyllithium, inpropyllithium, and n-propyllithium.
Examples include butyllithium, 5ec-butyllithium, isobutyllithium, n-pentyllithium, n-hexyllithium, and the like.

These may be used in combination of two or more types, or may be a mutual complex of two or more types. In order to exhibit the highest hydrogenation activity and selectively hydrogenate olefinically unsaturated double bonds in the living polymer, n-butyllithium is most preferred. ~------------
Although the present invention can be applied to all hydrocarbon living polymers polymerized with organolithium and having unsaturated double bonds in the polymer, a preferred embodiment is obtained by polymerizing or copolymerizing a conjugated diene. conjugated diene living polymer etch.

Such conjugated diene living polymers include living copolymers obtained by copolymerizing a conjugated diene homopolymer and a conjugated diene with each other or with at least one conjugated diene and at least one olefin monomer capable of living copolymerization with the conjugated diene. Included.

As the polymerization catalyst used for producing such a conjugated diene living polymer, a hydrocarbon having at least one lithium atom bonded in the molecule is used, such as n-propyllithium, inpropyllithium, n-butyllithium, 5ec. - Monolithium such as butyl pentalithium, tert-butyllithium, n-pentyllithium, benzyllithium, etc., or 1,4-dilithio-n-butane, 1,5-dilithiopentane, 1,2-dilithiodiphenylethane, 1 ,4-dilithio-1,1,4,4-
Tetraphenylbutane, 1,3- or 1,4-bis(
1-lithio-1,3-dimethylpentyl)benzene, 1
．． Dilithium such as 3- or 1,4-bis(1-lithio-3-methylpentyl)benzene is preferably used, and the polymerization catalyst is a lithium oligomer or α,ω-dilithium oligomer obtained with these organolithiums. It's okay. Particularly common examples include n-butyllithium, 5ec-butyllithium, and the like. These organolithiums may be used alone or in a mixture of two or more, and may be added not only once but also twice or more in the middle of the polymerization. The amount of organolithium to be used is appropriately selected depending on the molecular weight of the desired polymer.
Generally 0.0% based on the total amount of monomer used. OO'5 to 5 mol%.

Conjugated dienes used in the production of the conjugated diene living polymers to be subjected to hydrogenation of the present invention generally include conjugated dienes having from 4 to about 12 carbon atoms, and specific examples include 1, 3-butadiene, isoprene, 2
, 3-dimethyl-1,3-phtacyene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, ■, 3-
Examples include hexadiene, 4.5-diethyl-1,3-octadiene, 3-butyl-1,3-octadiene, and the like. From the viewpoint of obtaining a nidistomer that can be industrially advantageously developed and has excellent physical properties, 1,3-butadiene and isoprene are particularly preferred, and elastomers such as butadiene living polymer, isofrene living polymer, and butadiene/isoprene living copolymer are preferred. Particularly preferred for practicing the invention.

On the other hand, the method of the present invention is particularly suitably used for hydrogenating a living copolymer obtained by copolymerizing at least one conjugated diene and at least one monomer copolymerizable with the conjugated diene. Suitable conjugated dienes used in the production of such living copolymers include the conjugated dienes described above, and one monomer includes all monomers that can be living copolymerized with the conjugated diene, especially vinyl-substituted aromatic carbonized Hydrogen is preferred. In other words, in order to fully exhibit the effect of the present invention of selectively hydrogenating 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 living copolymers with vinyl-substituted aromatic hydrocarbons. Specific examples of vinyl-substituted aromatic hydrocarbons used in the production of such living copolymers include styrene, t-butylstyrene, α-methylstyrene, 0-methylstyrene, p-methylstyrene,
Examples include divinylbenzene, 1,1-diphenylethylene, vinylnaphthalene, N,N-dimethyl-p-amineethylstyrene, N,N-diethyl-p-amineethylstyrene, and styrene is particularly preferred. As specific examples of living copolymers, butadiene/styrene living copolymers, isoprene/styrene living copolymers, etc. are the most preferred since they provide hydrogenated copolymers with high industrial value.

In such a living copolymer, the vinyl-substituted aromatic hydrocarbon content is preferably 5% to 95% by weight; outside this range, it becomes difficult to obtain the characteristics of a thermoplastic elastomer.

Living copolymers according to the method of the invention include random copolymers, tapering block copolymers, complete block copolymers, and graft copolymers in which the monomers are statistically distributed throughout the polymer chain. In order to obtain industrially useful thermoplastic elastomers, living block copolymers having at least one conjugated diene polymer block and a small number (both one) of vinyl-substituted aromatic hydrocarbon polymer blocks are particularly important.

A preferred embodiment of the hydrogenation reaction of the present invention is carried out in a solution in which a living polymer is dissolved in an inert organic solvent, and more preferably in a solution obtained by polymerizing a conjugated diene or the like in an inert solvent. The hydrogenation reaction is carried out continuously as it is. "Inert organic solvent" means a solvent that does not react with any participant in the polymerization or hydrogenation reaction. Suitable solvents are, for example, n-pebutane,
These include aliphatic hydrocarbons such as n-hexane, n-hebutane and n-octane, alicyclic hydrocarbons such as cyclohexane and cycloheptane, and ethers such as diethyl ether and tetrahydrofuran, singly or in mixtures. Aromatic hydrocarbons such as benzene, toluene, xylene, ethylpenze/etc. can also be used as long as the aromatic double bonds are not hydrogenated under the selected hydrogenation reaction conditions. The hydrogenation reaction of the present invention is carried out at a living polymer concentration of 1 to 50% by weight, preferably 3 to 25% by weight relative to the solvent, so that the living polymer to be subjected to the hydrogenation reaction is not completely deactivated by moisture and impurities in the solvent. First, it is necessary to retain lithium.

The hydrogenation reaction of the present invention is generally carried out by maintaining a lubricating polymer solution at a predetermined temperature under hydrogen or an inert atmosphere, adding a hydrogenation catalyst with or without stirring, and then introducing hydrogen gas. This is carried out by applying pressure to a predetermined pressure.

An inert atmosphere means an atmosphere that does not react with any participants in the hydrogenation reaction, such as helium, neon, argon, and the like. Air and oxygen are not preferred because they oxidize or decompose the hydrogenation catalyst, leading to deactivation of the catalyst.

On the other hand, the catalyst was prepared in advance with catalyst component (B) and catalyst component (0
) is preferred because it has high activity. Although the hydrogenation reaction can be carried out by adding either catalyst component CB) or catalyst component (C) separately to the living polymer first, in order to obtain high activity, it is recommended to use a mixture in advance. preferable.

It is necessary to handle the catalyst component (C) under the above-mentioned inert atmosphere. Although catalyst component ω) is stable in air, it is preferable to handle it under an inert atmosphere.

Further, although each catalyst component may be used as it is, it is preferable to use it as a solution of the inert organic solvent because it is easier to handle. As the inert organic solvent used when the solution is used, the various solvents mentioned above that do not react with any of the participants in the hydrogenation reaction can be used. Preferably, it is the same solvent as used in the hydrogenation reaction.

When premixing the catalyst components or adding the catalyst components to the hydrogenation reactor, it is most preferable to do so under a hydrogen atmosphere. When catalyst component ω) and catalyst component (C) are mixed in advance and used, they are prepared at a temperature of -30°C to 100°C, preferably at a temperature of -10°C to 50°C immediately before the hydrogenation reaction. However, if it is stored under a hydrogen atmosphere or an inert atmosphere, it can be used without changing its substantial hydrogenation activity even at room temperature for about one week.

When the catalyst components are added in advance, the mixing ratio of each catalyst component to achieve high hydrogenation activity and hydrogenation selectivity is as follows:
Catalyst component (C) mole number of glue and catalyst component a'3)
The ratio of the number of moles of titanium to the number of moles of titanium (hereinafter referred to as L1/T4 mole ratio) is in the range of about 20 or less. Quantitative hydrogenation can be carried out even at a Li710 molar ratio -〇, but it requires higher temperature and higher pressure conditions, and at a L]/T1 molar ratio of 20 or more, an expensive catalyst is used which does not substantially improve the activity. component(
Preferably, 1. Excessive use of O is not only uneconomical but also tends to cause unnecessary side reactions. <No. L
A range of i/T emole ratio of 0.5 to 1O is most suitable for significantly improving hydrogenation activity.

In addition, in the hydrogenation reaction of the living polymer according to the present invention, since reducing lithium is also present in the living polymer, the amount of lithium in the catalyst component (0) is added to the amount of lithium in the living polymer during the hydrogenation reaction. The ratio of the total amount of lithium and the titanium of the catalyst component (J3) influences the hydrogenation activity. In order to achieve high hydrogenation activity and high hydrogenation selectivity for unsaturated double bonds in conjugated diene units,
The ratio of the total number of moles of lithium in the hydrogenation reaction system to the number of moles of titanium in the catalyst component (B) (hereinafter referred to as the total Li/T 1 mole ratio) is in the range of about 05 to 25. Furthermore, all T, i/T
An emole ratio in the range of 1 to 15 is optimal because it significantly improves hydrogenation activity.

The amount of lithium in the living polymer varies depending on the molecular weight of the lubricating polymer, the functional number of the organic lithium used as a polymerization catalyst, and the deactivation rate of the living polymer, and the above total L x
/T-1 molar ratio, it is necessary to deactivate a part of the living polymer in advance with water, alcohol, a norogen compound, etc., or add a catalyst component (C
) is added in advance to adjust the total lithium concentration.

On the other hand, the amount of hydrogenation catalyst added is preferably in the range of 0.005 to 20 mmol per 100 g of the peeling polymer. Within this addition amount range, it is possible to preferentially hydrogenate the unsaturated double bonds of the conjugated diene units of the living polymer, and hydrogenation of the aromatic nucleus double bonds does not substantially occur, so the hydrogenation rate is extremely high. Hydrogenation selectivity is achieved. Hydrogenation of the living polymer is possible even when adding 20 mmol or more,
Although this does not limit its use, the hydrogenation effect does not substantially change even if 20 mmol or more is added; on the contrary, using more catalyst than necessary is not only uneconomical, but also increases the hydrogenation reaction time. Demineralization and removal of minerals are required, which leads to disadvantages such as complicating the process. Further, if the amount is less than 0.005 mIJ mole, the catalyst is likely to be deactivated due to impurities and the like, making it difficult to proceed with quantitative hydrogenation.

More preferred amount of hydrogenation catalyst added is 100
It ranges from 9005 to 5 mmol per I.

The hydrogenation reaction of the present invention is carried out using elemental hydrogen, more preferably introduced in gaseous form into the living polymer solution. 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 0°C to 150°C.

If it is below 0°C, the activity of the catalyst decreases and the hydrogenation rate becomes slow, requiring a large amount of catalyst, which is not economical, and the hydrogenated polymer tends to become insolubilized and precipitate. On the other hand, a temperature of 150° C. or higher is not preferable because it causes deactivation of the catalyst, tends to cause decomposition and gelation of the polymer, and also tends to cause hydrogenation of the aromatic nucleus portion, resulting in a decrease in hydrogenation selectivity. More preferably, the temperature is in the range of 20 to 120°C.

Although the pressure of hydrogen used in the hydrogenation reaction is not particularly limited, it is preferably 1 to 100 kg/CIrL2.

If it is less than 1 kg/crfL2, the hydrogenation rate slows down and practically reaches a plateau, making it difficult to increase the hydrogenation rate.
At 100 kg/cyn2 or more, the hydrogenation reaction is almost completed at the same time as the pressure is increased, which is essentially meaningless, and unnecessary side reactions and gelation are caused, which is not preferable. A more preferable hydrogenation pressure is 2 to 30 kg/cIrL2, but the optimum hydrogen pressure is selected in correlation with the hydrogenation conditions such as the amount of catalyst added, and in practice, the hydrogen pressure decreases as the amount of hydrogenation catalyst decreases. It is preferable to select the high pressure side for implementation.

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

The hydrogenation reaction of the present invention may be carried out in any manner such as batchwise or continuous. 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 conjugated diene units of the polymer are hydrogenated. More preferably, when a copolymer of a conjugated diene and a vinyl-substituted aromatic hydrocarbon is hydrogenated, the hydrogenation rate of unsaturated double bonds in the conjugated diene unit is 50% or more, preferably 90% or more, and the aromatic nucleus It is possible to obtain selectively hydrogenated hydrogenated copolymers with a partial hydrogenation degree of 10% or less. If the hydrogenation rate of the conjugated diene unit is less than 50%, the effects of improving weather resistance, oxidation resistance, and heat resistance will not be sufficient. In addition, in the case of a copolymer of a conjugated diene and a vinyl-substituted aromatic hydrocarbon, no significant property improvement effect was observed even if the aromatic nucleus moiety was hydrogenated.
In particular, block copolymers have excellent processability,
Formability deteriorates. Furthermore, hydrogenation of the aromatic nucleus portion consumes a large amount of hydrogen and requires a hydrogenation reaction at high temperature, high pressure, and for a long time, making it difficult to carry out economically. The polymer hydrogenation catalyst according to the present invention has extremely excellent selectivity, and the aromatic nucleus portion is not substantially hydrogenated, so that it is extremely advantageous industrially.

If necessary, catalyst residues can be removed from the polymer solution subjected to the hydrogenation reaction by the method of the present invention, and the hydrogenated polymer can be easily isolated from the solution. For example, a method in which a polar solvent such as acetone or alcohol, which is a poor solvent for the hydrogenated polymer, is added to the reaction solution after hydrogenation to precipitate and recover the polymer, or a method in which the reaction solution is stirred and poured into boiling water, and then distilled and recovered together with the solvent. This can be carried out by a method of directly heating the reaction solution and distilling off the solvent.

The hydrogenation method of the present invention is characterized in that the amount of hydrogenation catalyst used is small. Therefore, even if the hydrogenation catalyst remains in the polymer, it does not significantly affect the physical properties of the hydrogenated polymer obtained, and most of the catalyst is decomposed and removed during the isolation process of the hydrogenated polymer and is removed from the polymer. Therefore, no special operations are required to deash or remove the catalyst, and it can be carried out in an extremely simple process.

〔Effect of the invention〕

As described above, according to the present invention, a conjugated diene polymer can be hydrogenated under mild conditions using a highly active catalyst, and in particular, unsaturated double bonds in a conjugated diene unit of a copolymer of a conjugated diene and a vinyl-substituted aromatic hydrocarbon can be hydrogenated. It became possible to hydrogenate extremely selectively. Furthermore, in the method of the present invention, since a living polymer is used as a raw material, hydrogenation can be carried out continuously in the same reactor following polymerization, and only one type of catalyst component is required, and even a small amount can be added. It exhibits high activity and therefore does not require deashing of the catalyst after hydrogenation, making it possible to carry out the process efficiently in an economical and simple process, which is extremely useful industrially.

Furthermore, the hydrogenated polymer obtained by the method of the present invention is
It is used as an elastomer, thermoplastic nidistomer, or thermoplastic resin with excellent weather resistance and oxidation resistance, and it can also be used with additives such as ultraviolet absorbers, oils, and fillers.
It is used in blends with other nidistomers and resins, and is extremely useful industrially.

〔Example〕

EXAMPLES The present invention will be specifically explained below with reference to Examples, but the present invention is not limited thereto.

Synthesis examples of each hydrogenation catalyst and each living polymer used in the examples are shown in the following reference examples.

Reference Example 1 200 ml of anhydrous ether was added to an 11-three-hole flask equipped with a stirrer, a dropping funnel, and a reflux condenser. Replace the device with dry helium and add 17.4 pieces of lithium wire.
g (2.5 mol) in a flask and 300 ml of ether. A small amount of a solution of bromobenzene 157!9 (1 mol) was added dropwise at room temperature, and then the entire amount of the ethereal solution of bromobenzene was added to the stalks under reflux.

After the reaction was completed, the reaction solution was filtered under a helium atmosphere to obtain a colorless and transparent phenyllithium solution.

21 with a stirrer and a dropping funnel replaced with dry helium.
99.6 g (0.4 mol) of dichlorobis(cyclopentadienyl)titanium and 500 ml of anhydrous ether were added to a Mitsuro flask. The previously synthesized ether solution of phenyllithium was added dropwise at room temperature under stirring for about 2 hours. The reaction mixture was separated in air/air, and after washing the insoluble portion with dichloromethane, the p solution and washing solution were combined and the solvent was removed under reduced pressure. After dissolving the residue in a small amount of dichloromethane, petroleum ether was added to perform recrystallization. The obtained crystals were separated, the p liquid was concentrated again, and the above operation was repeated to obtain diphenylbis(η-cyclopentadienyl)titanium. Yield: 120g (yield 90%)
)Met. The obtained crystals were orange-yellow needle-shaped, had good solubility in toluene and cyclohexane, had a melting point of 147°C, and had an elemental analysis value of 0. 79.5;E,
6.1; Ti, 14.4.

Reference Example 2 Di-p-tolylbis (η
-cyclopentagenyl) titanium was obtained (yield 87
%). This substance is in the form of yellow crystals, has good solubility in ants, toluene, and cyclohexane, has a melting point of 145°C,
Elemental analysis value: C, 80,0; H, 6,7iTi, 13.
It was 3.

Reference Example 3 Synthesis was carried out in the same manner as in Reference Example 1 except that 4-bromo-0-xylene was used instead of bromobenzene, to obtain g. 83%). This substance is in the form of yellow crystals, has good solubility in toluene and cyclohexane, has a melting point of 155°C, and has an elemental analysis value of C, 80, 6; u, '7,
2; Ti, 12.2.

Reference Example 4 Synthesis was carried out in the same manner as in Reference Example 1 except that p-bromoethylbenzene was used instead of bromobenzene to obtain bis(4-ethylphenyl)bis(η-cyclopentajenyl)titanium (yield: 80%).

This substance is a yellow crystal, has good solubility in toluene and cyclohexane, has a melting point of 154°C, and has an elemental analysis value of 0.80.4 iH, 7,3i Ti.

It was 12.3.

Reference Example 5 Cyclohexane 5009.1 in an autoclave of 21
．． 100 g of 3-butadiene monomer and 0.05 g of n-butyllithium were added, and polymerization was carried out at 60° C. for 3 hours with stirring to synthesize living polybutadiene.

The living polybutadiene obtained was 0.00 g/100 g of polymer. When it was partially isolated and analyzed, it was found to be a living polybutadiene containing 13% of 1,2-vinyl bonds and having a number average molecular weight of about 150,000 as measured by GPO.

Reference Example 6 A living polymer 100. l
with 066 mmol of living lithium per i′ and 1
, 10% of 2-vinyl bonds and a number average molecular weight of about 150,000 were obtained.

Reference Example 7 400 g of cyclohexane, 70.9 g of 1,3-butadiene monomer. Styrene monomer 309, n-butyllithium 0.03. ! i+ and tetrahydrofuran 09g
were simultaneously added to the autoclave and polymerized at 40°C for 2 hours.

The resulting polymer is a completely random living copolymer of butadiene/styrene with a concentration of 0.4/100 I of polymer.
It has 8 mmol of living lithium, 1,2-vinyl bond content of butadiene unit is 50%, and number average molecular weight is 20.
He had 10,000,000.

Reference Example 8 400 g of cyclobexane, 15 g of styrene monomer and 0.11 g of n-butyllithium were added to an autoclave and polymerized at 60°C for 3 hours, then 709% of 1,3-butadiene monomer was added and polymerized at 60°C for 3 hours. did. Finally, 15 g of styrene monomer was added and polymerized for 3 hours at 60°C. The content of bound styrene 7 was 30%, the content of blocked styrene was 29.5%, and the content of 1,2-vinyl bound gold in butadiene units was 13% (total A styrene-butadiene-styrene type living block copolymer having a number average molecular weight of about 60,000 (9% in terms of polymer) was obtained. The living lithium in this polymer was 1.65 mmol/100 g of polymer.

Reference Example 9 Polymerization was carried out in exactly the same manner as in Reference Example 5, except that 35 times the mole of tetrahydrofuran was added to n-butyllithium, and the content of bound styrene was 30%, the content of blocked styrene was 25%, and the 1,2- A styrene-butadiene-styrene type living Glock polymer having a vinyl bond content of 38% and a number average molecular weight of approximately 60,000 was synthesized. The living lithium content in this polymer was 165 mmol/100 g of polymer.

Reference example work 0 400 ml of cyclohexane in an autoclave. ! l/.

1.3-butadiene monomer 13.91 n-butyllithium 0.15,! 9 and tetrahydrofuran at a molar ratio of n -BuLi/'rHF = 40, polymerization was carried out at 70 °C for 45 minutes, then 2 ° g of styrene monomer was added for 30 minutes, and then 47 g of 1,3-butadiene monomer was added. Then, 20 g of styrene monomer was added and polymerized for 30 minutes to synthesize a butadiene-styrene-butadiene-styrene type living Glock polymer.

This material has a bound styrene content of 40%, a blocked styrene content of 33%, a 1.2-vinyl bond content of butadiene units of 35% (30% in terms of total polymer), a number average molecular weight of approximately 60,000, and a living polymer. It had 1.65 mmol of living lithium per 100 g.

Examples 1 to 4 The ping polymer solution obtained in Reference Example 8 was diluted with purified and dried cyclohexane to give a living polymer concentration of 1.
It was adjusted to 0% by weight and subjected to hydrogenation reaction.

In a sufficiently dry autoclave with a capacity of 21 and equipped with a stirrer, 1,000 ml of the above living polymer solution was added. ! Prepare 9,
After degassing under reduced pressure, the mixture was replaced with hydrogen and maintained at 60° C. with stirring.

Next, 100 cyclohexane solutions each containing 0.8 mmol of the compounds obtained in Reference Examples 1 to 4 as catalyst component ω) were prepared.
rnl and n-butyllithium (C) as the catalyst component (C).
20 ml of a cyclohexane solution containing 0.16 mmol (manufactured by Honjo Chemical Co., Ltd.) was mixed for about 15 minutes at 0°C in a hydrogen atmosphere of 2.0 kg/cm2. cm2 of dry gaseous hydrogen was supplied, and the hydrogenation reaction was carried out for 1 hour with stirring. The reaction solution was returned to normal temperature and pressure, taken out from the autoclave, poured into a large amount of methanol to precipitate the polymer, and dried separately to obtain a white hydrogenated polymer. The hydrogenation rate of the obtained hydrogenated polymer was determined from an infrared spectrum (details of how to determine the hydrogenation rate are described in Japanese Patent Application No. 58-6718) and are shown in Table 1.

Examples 5 to 9 Water was prepared in the same manner as in Example 1 except that the living polymer of Reference Example 5.6.7.9.10 was used and the compound obtained in Reference Example 2 was used as the catalyst component (J3). An addition reaction was performed. The results are shown in Table I.

Examples 10 to 16 The amount of n-butyllithium when pre-mixing catalyst components (J3) and (0) was set to n-BuLi/T shown in Table 3.
Add methanol in an amount to deactivate part of the living lithium in advance to the reactor so that the total Li/T molar ratio shown in Table 1 is achieved during the hydrogenation reaction. A hydrogenation reaction was carried out in exactly the same manner as in Reference Example 2, except that n-butyllithium was added.

The results are shown in Table H.

Examples 17 to 25 Example 10 was carried out under the conditions shown in Table 1 using the phosphorus polymer obtained in Reference Example 8, the hydrogenation catalyst component Cl5) obtained in Reference Example 2, and n-butyllithium. The hydrogenation reaction was carried out in the same manner as in 16.

The results are shown in Table ■.

Procedural amendment November 9, 1982

Claims (1)

[Scope of Claims] 1. A method of hydrogenating a living polymer containing an olefinically unsaturated group in an inert organic solvent, wherein (A) a conjugated diene is polymerized or copolymerized with a conjugated diene using an organolithium as a polymerization catalyst. (B) At least one titanocene diaryl compound shown in (a) below ▲ There are numerical formulas, chemical formulas, tables, etc. ▼ (a) (However, R_1 to R_6 are Represents hydrogen or an alkyl hydrocarbon group having 1 to 4 carbon atoms, R_1 to R_3 and R_
One or more of 4 to R_6 is hydrogen. ) and (C) general formula R-Li (wherein R has 1 to 6 carbon atoms)
represents an alkyl group. ) The unsaturated double bonds of the conjugated diene units in the living polymer are selectively hydrogenated by contacting with hydrogen in the presence of a catalyst comprising at least one alkyllithium compound represented by Hydrogenation method for living polymers.