JP2008150504A - Process for producing halogen-containing saturated polyolefin - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a process for efficiently producing a halogen-containing saturated polyolefin suitably used as a raw material for industrial parts by the hydrogenation of a halogen-containing unsaturated polyolefin which has been difficult by the conventional method. <P>SOLUTION: The process for producing a halogen-containing saturated polyolefin useful as a starting material for various types of industrial parts comprises hydrogenating a halogen-containing unsaturated polyolefin in the presence of an organic solvent, hydrazine, and oxygen with the use of a flavin compound as a hydrogenating catalyst. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a method for producing a halogen-containing saturated polyolefin, and particularly as a raw material for various industrial parts by hydrogenating a halogen-containing unsaturated polyolefin using a flavin compound in the presence of an organic solvent, hydrazine and oxygen. The present invention relates to a method for producing a useful halogen-containing saturated polyolefin.

  As for hydrogenation of halogen-containing unsaturated polyolefin, a method of hydrogenating chloroprene with hydrogen using a ruthenium or rhodium complex as a catalyst has been reported (for example, see Patent Document 1 and Non-Patent Document 1).

  On the other hand, in recent years, a method for hydrogenating olefins using flavin as a catalyst and under mild conditions with oxygen and hydrazine has been reported (for example, Non-Patent Document 2).

JP 2002-128822 A Macromolecules, vol. 27, p. 6985-6987 (1994) Journal of American Chemical Society Vol. 127, no. 42, p. 14544-14545 (2005)

  However, in the methods disclosed in Patent Document 1 and Non-Patent Document 1, since the reaction is carried out at a high hydrogen pressure, an expensive reactor is required, and there are still problems industrially. No. 1 states that a dehalogenation reaction occurs during the hydrogenation reaction, and corrosion of the apparatus becomes a problem. Thus, hydrogenation of halogen-containing unsaturated polyolefin using hydrogen has many industrial problems.

  On the other hand, the method disclosed in Non-Patent Document 2 is an industrially preferable method in that olefins can be hydrogenated under mild conditions. However, an aqueous solvent that is easily miscible with hydrazine as a reducing agent and pure oxygen are used. The hydrogenation of low molecular weight olefin compounds, such as unsaturated polyolefins that are difficult to dissolve in aqueous media, especially the hydrogenation of unsaturated polyolefins that contain halogen elements that are difficult to hydrogenate. Currently, no knowledge is available.

  Accordingly, the present invention provides a method for efficiently hydrogenating a halogen-containing unsaturated polyolefin and producing a halogen-containing saturated polyolefin useful as various industrial parts.

  As a result of intensive studies to solve the above problems, the present inventors have conducted a method of hydrogenating a halogen-containing unsaturated polyolefin using a flavin compound as a hydrogenation catalyst, particularly in the presence of an organic solvent, hydrazine, and oxygen. It has been found that by using a flavin compound as a hydrogenation catalyst and hydrogenating a specific halogen-containing unsaturated polyolefin, it becomes possible to produce an excellent halogen-containing saturated polyolefin efficiently, and the present invention is completed. It came to.

  That is, the present invention is characterized in that a halogen-containing unsaturated polyolefin is hydrogenated using a flavin compound represented by the following general formula (1) as a hydrogenation catalyst in the presence of an organic solvent, hydrazine and oxygen. The present invention relates to a method for producing a halogen-containing saturated polyolefin.

(1)
(Wherein R ₁ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a phenylalkyl group having 7 to 12 carbon atoms, and R ₂ and R ₃ are each independently a hydrogen atom, 1 to 1 carbon atom) 10 represents an alkyl group or an alkoxy group, R ₄ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group, a 2,4: 3,5-di-o-methyleneribityl group, or a phenyl group; R ₅ represents an alkyl group having 1 to 10 carbon atoms and a phenylalkyl group having 7 to 12 carbon atoms.)
The present invention is described in detail below.

  The method for producing a halogen-containing saturated polyolefin according to the present invention comprises the step of hydrogenating a halogen-containing unsaturated polyolefin using the flavin compound represented by the above general formula (1) as a hydrogenation catalyst to produce the halogen-containing saturated polyolefin. In addition, the hydrogenation reaction is performed in the presence of an organic solvent, hydrazine and oxygen.

The hydrogenation catalyst in the present invention is a flavin compound represented by the above general formula (1), and a flavin compound having any structure can be used as long as it belongs to the category. Here, R ₁ is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a phenylalkyl group having 7 to 12 carbon atoms, and more specifically, for example, a hydrogen atom, a methyl group, an ethyl group, a propyl group, Isopropyl group, butyl group, isobutyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, benzyl group, phenylethyl group, phenylpropyl group, phenylbutyl group, phenylpentyl group, phenylhexyl group, etc. Can be mentioned. R ₂ and R ₃ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group, and more specifically, for example, a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, Examples thereof include a butyl group, an isobutyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group. R ₄ is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group, a 2,4: 3,5-di-o-methyleneribityl group, or a phenyl group, and more specifically, for example, a methyl group, Ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, benzyl, 2-phenylethyl, 3-phenylpropyl, 4- Examples thereof include a phenylbutyl group, a 5-phenylpentyl group, a 6-phenylhexyl group, a 2,4: 3,5-di-o-methyleneribityl group, and the like. R ₅ is an alkyl group having 1 to 10 carbon atoms or a phenylalkyl group having 7 to 12 carbon atoms, and more specifically, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, Pentyl group, benzyl group, 2-phenylethyl group, 3-phenylpropyl group, 4-phenylbutyl group, 5-phenylpentyl group, 6-phenylhexyl group, phenyl group, 2-methylphenyl group, 3-methylphenyl group 4-methylphenyl group, 2-methoxyphenyl group, 3-methoxyphenyl group, 4-methoxyphenyl group, and the like.

  Specific examples of the flavin compound include 5-ethyl-3,7,8,10-tetramethylisoalloxazinium perchlorate, 5-ethyl-7,8,10-trimethylisoalloxazinium park. Lorate, 5-ethyl-3-methyl-10-phenylisoalloxazinium perchlorate, 5-ethyl-3,10-dimethylisoalloxazinium perchlorate, 5-ethyl-3,7,8-trimethyl-10- (2 ′, 4 ′: 3 ′, 5′-di-o-methyleneribityl) isoalloxazinium perchlorate can be exemplified, and among them, particularly, since the hydrogenation efficiency of the halogen-containing unsaturated polyolefin is excellent, 5-ethyl-3,7,8-trimethyl-10- (2 ′, 4 ′: 3 ′, 5′-di-o-methyleneribityl) isoallo It is preferably a spoon perchlorate and / or 5-ethyl -3,7,8,10- tetramethyl iso Aroki spoon perchlorate.

  The flavin compound may be obtained and produced by any method as long as the object of the present invention can be achieved, for example, Angew. Chem. Int. Ed. 44, 1704-1706 (2005).

  The amount of the flavin compound used in the present invention may be any amount as long as the halogen-containing unsaturated polyolefin can be hydrogenated, and among them, the halogen-containing unsaturated polyolefin can be efficiently hydrogenated. Therefore, the content is preferably in the range of 0.0001 mol% to 30 mol%, particularly 0.01 mol% to 5 mol% with respect to 1 mol of the halogen-containing unsaturated polyolefin.

  As the halogen-containing unsaturated polyolefin used in the present invention, a halogen-containing unsaturated polyolefin having any structure can be used as long as it has a halogen element and an unsaturated bond in the polymer structure.

  Examples of such halogen-containing unsaturated polyolefins include olefin metathesis polymers containing halogen elements such as 5-norbornene-2,3-bischloromethyl; halogen elements such as chloroprene rubber and chloroprene-butadiene copolymer. The polymer of the conjugated diene to contain can be illustrated.

The halogen-containing unsaturated polyolefin has a weight measured by gel permeation chromatography (GPC) in terms of standard polystyrene because the resulting halogen-containing saturated polyolefin has particularly excellent molding processability and mechanical properties. The average molecular weight is preferably in the range of 1 × 10 ³ to 1 × 10 ⁶ , and particularly preferably in the range of 1 × 10 ^{4 to} 5 × 10 ⁵ .

  The solvent used in the present invention can be used without any limitation as long as it is an organic solvent and belongs to the above category, and among them, a solvent that dissolves a halogen-containing unsaturated polyolefin is preferable. Since halogenated unsaturated polyolefin can be hydrogenated particularly efficiently, dichloromethane, chloroform, 1,1-dichloroethane, 1,2-dichloroethane, 1,1,2-trichloroethane, 1,1,1-trichloroethane, Halogen solvents such as 1,1,2,2-tetrachloroethane, chlorobenzene, 1,2-dichlorobenzene and 1,3,5-trichlorobenzene, and aromatic solvents such as toluene and xylene are preferred.

  The hydrazine used in the present invention may be in any form as long as it is hydrazine, and is usually used as a monohydrate, but may be used after being arbitrarily diluted with a solvent or water in addition to an anhydride. it can. The amount of hydrazine used may be any amount as long as the halogen-containing unsaturated polyolefin can be hydrogenated, and 0.1 mol to 1 mol of olefin in the halogen-containing unsaturated polyolefin. The range is preferably 20 mol, and particularly preferably in the range of 0.5 mol to 10 mol.

  In addition, as a method for adding hydrazine, a method of adding a predetermined amount to a solution comprising a halogen-containing unsaturated polyolefin and an organic solvent at once; a sequential addition method of adding dropwise as necessary, and further adding during the reaction as needed Any method may be used. In general, hydrazine and an organic solvent often do not dissolve, and in the production method of the present invention, the reaction system becomes non-uniform due to the addition of hydrazine, and the heterogeneous hydrogenation reaction often proceeds. It can be seen.

  The oxygen used in the present invention is not only pure oxygen but also any mixed gas composed of air, a mixture of air and pure oxygen, or an inert gas such as pure oxygen and nitrogen, helium, or argon. Among them, it is preferable to use air as an oxygen source.

  Although the production method of the present invention can be carried out even under atmospheric pressure, it is preferably carried out under pressure conditions because of its excellent hydrogenation reaction efficiency. The pressure at the time of pressurization is 0.01 MPa to A range of 0.99 MPa is preferable, and a range of 0.1 MPa to 0.6 MPa is particularly preferable. The reaction temperature may be any temperature as long as a hydrogenation reaction is possible, and is particularly preferably in the range of 20 to 200 ° C., particularly in the range of 50 to 150 ° C., because of excellent hydrogenation reaction efficiency. Preferably there is.

  The halogen-containing saturated polyolefin obtained by the production method of the present invention can be recovered by charging the solution after completion of the reaction into a poor solvent and reprecipitation. Here, the poor solvent can be used without particular limitation as long as the halogen-containing saturated polyolefin can be reprecipitated. For example, alcohols such as methanol and ethanol; ethers such as diethyl ether and tetrahydrofuran; acetone and methyl ethyl ketone And ketones such as methyl acetate and esters such as methyl acetate and ethyl acetate. Methanol is preferred because of its particularly excellent recovery of halogen-containing saturated polyolefins.

  By the hydrogenation of halogen-containing unsaturated polyolefins that were difficult to hydrogenate by conventional methods, the method of the present invention enables efficient production of halogen-containing saturated polyolefins that are useful as raw materials for various industrial parts. It becomes.

  EXAMPLES Hereinafter, although an Example demonstrates this invention, a present Example does not restrict | limit this invention at all.

<Analysis / Measurement>
-Measurement of number average molecular weight and weight average molecular weight-
Using gel permeation chromatography (GPC) (trade name HLC8020GPC, manufactured by Tosoh Corporation), the number average molecular weight and the weight average molecular weight are measured as standard polystyrene conversion values from an elution curve measured at 40 ° C. using chloroform as a solvent. did.

~ Measurement of NMR spectrum ~
Using a nuclear magnetic resonance spectrum measuring apparatus (trade name GSX270WB, manufactured by JEOL Ltd.), measurement was performed using deuterated chloroform as a heavy solvent.

~ Measurement of IR ~
Measurement was performed using an infrared spectrophotometer (trade name 270-30 type infrared spectrophotometer manufactured by Hitachi, Ltd.).

~ Measurement of UV-Vis ~
Measurement was performed using an ultraviolet-visible spectrophotometer (manufactured by JASCO, product name UVIDEC-650).

Synthesis Example 1 (Synthesis of 5-ethyl-3,7,8-trimethyl-10- (2 ′, 4 ′: 3 ′, 5′-di-o-methyleneribityl) isoalloxazinium perchlorate)
<Synthesis of 7,8-dimethyl-10- (2 ′, 4 ′: 3 ′, 5′-di-o-methyleneribityl) isoalloxazine>
In a 200 ml flask equipped with a magnetic rotor, 9.4 g of riboflavin (manufactured by Tokyo Chemical Industry) was taken, and 15 ml of concentrated hydrochloric acid and 23 ml of 37% formalin solution were added. The mixture was heated and stirred at 60 ° C. for 48 hours under a nitrogen atmosphere. The dark brown solution after the reaction was concentrated under reduced pressure using an evaporator and then vacuum dried under reduced pressure of 1 mmHg for 2 hours to obtain 15.6 g of a blackish brown powder.

  This black-brown powder was subjected to column purification with 400 g of neutral alumina (Merck) using methanol as an eluent, and methanol was removed under reduced pressure to obtain 4.4 g of a yellow powder.

The obtained yellow powder was confirmed to be 7,8-dimethyl-10- (2 ′, 4 ′: 3 ′, 5′-di-o-methyleneribityl) isoalloxazine by ¹ H-NMR spectrum analysis. .

Measurement result of 270 MHz ¹ H-NMR; δ (CDCl ₃ ): 2.44 (3H), 2.55 (3H), 3.54 to 3.61 (3H), 4.17 to 4.30 (2H) 4.62-4.69 (2H), 4.91-5.10 (4H), 7.56 (1H), 8.06 (1H).

<Synthesis of 3,7,8-trimethyl-10- (2 ′, 4 ′: 3 ′, 5′-di-o-methyleneribityl) isoalloxazine>
To a 1 liter four-necked flask equipped with a magnetic rotor, 15.2 g of potassium carbonate (manufactured by Wako Pure Chemical Industries) and 1000 ml of dimethylformamide (manufactured by Wako Pure Chemical Industries) were added. After dissolving 4.4 g (10.9 mmol) of 7,8-dimethyl-10- (2 ′, 4 ′: 3 ′, 5′-di-o-methyleneribityl) isoalloxazine synthesized in this slurry solution, iodination was performed. 6.9 ml (0.11 mol) of methyl (manufactured by Kanto Chemical) was added by syringe. After adding methyl iodide, the mixture was stirred at room temperature for 24 hours. After completion of the reaction, excess potassium carbonate was removed by suction filtration, and dimethylformamide was removed under reduced pressure from the obtained dimethylformamide solution with an evaporator to obtain 5.2 g of a brown liquid. The resulting brown liquid was subjected to column purification with 200 g of neutral alumina (manufactured by Merck) using chloroform as an eluent to obtain 1.65 g of a yellow powder.

The obtained yellow powder is 3,7,8-trimethyl-10- (2 ′, 4 ′: 3 ′, 5′-di-o-methyleneribityl) isoalloxazine by ¹ H-NMR spectrum analysis. confirmed.

270 MHz ¹ H-NMR measurement results; δ (DMSO-d6): 2.44 (3H), 2.55 (3H), 3.52 (3H), 3.54 to 3.61 (3H), 4. 17-4.30 (2H), 4.62-4.69 (2H), 4.91-5.10 (4H), 7.56 (1H), 8.06 (1H).

<Synthesis of 5-ethyl-3,7,8-trimethyl-10- (2 ′, 4 ′: 3 ′, 5′-di-o-methyleneribityl) isoalloxazinium perchlorate>
To a 300 ml four-necked flask equipped with a magnetic rotor, 3.36 g (0.05 mol) of sodium cyanotrihydroborate (manufactured by Wako Pure Chemical Industries) was taken, and after purging the inside of the four-necked flask with nitrogen, a nitrogen atmosphere was created. . Dissolve 2.1 g of 3,7,8-trimethyl-10- (2 ′, 4 ′: 3 ′, 5′-di-o-methyleneribityl) isoalloxazine using 80 ml of dimethylformamide and transfer to a four-necked flask. did. Further, 40 ml of dimethylformamide was added, and then 1.5 ml of acetic acid (manufactured by Wako Pure Chemical Industries) was added with a syringe. Finally, 25 g (0.5 mol) of a 90% acetaldehyde (manufactured by Wako Pure Chemical Industries) solution was added all at once, and the internal temperature was adjusted to 60 ° C. using an oil bath. The mixture was stirred at the same temperature for 2 hours to obtain a yellow slurry. The reaction solution was allowed to cool to room temperature, and extracted with 300 ml of water and 600 ml of chloroform. The chloroform solution was further washed with 300 ml of saturated saline. Chloroform and dimethylformamide were distilled off from the resulting chloroform solution under reduced pressure. The obtained residue was dissolved in ethanol, a 10% aqueous ammonia solution was further added, and the mixture was cooled to 0 ° C. At 0 ° C., 60 ml of 4 mol / liter perchloric acid aqueous solution, 1.4 g of sodium nitrite and 3.1 g of sodium perchlorate were added to the mixture. The resulting purple slurry was returned to room temperature and stirred for 2 hours, and then filtered to give 5-ethyl-3,7,8-trimethyl-10- (2 ′, 4 ′: 3 ′, 5′-di- 1.1 g of (o-methyleneribityl) isoalloxazinium perchlorate was obtained as a purple powder.
Melting point measurement result: 206-208 ° C
UV measurement result: (CH ₃ CN) λmax 418 nm, 559 nm
IR measurement result: (KBr) 1710, 1650, 1600, 1560, 1460, 1440, 1360, 1180, 1120, 1100 (cm ⁻¹ ).

Synthesis Example 2 (Synthesis of 5-ethyl-3,7,8,10-tetramethylisoalloxazinium perchlorate)
Liebig Anarlen Dale Chemie, p. 1388 to 1415 (1973), and synthesis was performed to obtain 0.35 g of 5-ethyl-3,7,8,10-tetramethylisoalloxazinium perchlorate as a reddish purple powder.
Melting point measurement result: 220-225 ° C
UV measurement result: (CH ₃ CN) λmax 412 nm, 555 nm
IR measurement result: (KBr) 1700, 1650, 1100 (cm ⁻¹ ).

Synthesis example 3
A 2-liter SUS autoclave equipped with a stirrer, a thermometer, and a nitrogen introduction tube was charged with 800 g of 1,4-dichloro-2-butene and 212 g of dicyclopentadiene, and the system was sufficiently replaced with nitrogen. The Diels-Alder reaction was carried out at a reaction temperature of 170 ° C. for 4 hours.

  The obtained reaction liquid was distilled under a reduced pressure of 0.4 kPa to obtain 280 g of a fraction at 80 ° C. to 93 ° C.

This fraction was a pale yellow liquid and was confirmed to be 5-norbornene-2,3-bischloromethyl by ¹ H-NMR spectrum and GC-MS.

  Next, the 100 ml Schlenk tube containing the magnetic rotor was dried with a heat gun under reduced pressure, and sufficiently substituted with nitrogen. Here, 21 mg (25 μmol) of a ruthenium complex represented by the following general formula (2) was added. To this Schlenk tube, 46 ml of dry chloroform and 34 mg (0.25 mmol) of phenyl vinyl sulfide were weighed with a syringe to prepare a metathesis polymerization catalyst solution. Next, 3.8 g (25 mmol) of 5-norbornene-2,3-bischloromethyl synthesized previously was charged, and immersed in an oil bath adjusted to 60 ° C. for polymerization for 5 hours.

  Thereafter, the polymerization solution was poured into 150 ml of methanol containing 0.1% of 2,6-di-t-butyl-4-hydroxytoluene to precipitate a polymer. After filtration, the recovered polymer was dried in a vacuum dryer at room temperature for 8 hours to obtain 3.5 g of polymer.

The obtained polymer was confirmed to be a ring-opening metathesis polymer of 5-norbornene-2,3-bischloromethyl by ¹ H-NMR spectrum analysis.

270 MHz ¹ H-NMR measurement result; δ (CDCl ₃ ): 1.4 to 3.6 (10H), 5.2 to 5.6 (2H)
The weight average molecular weight (Mw) of this polymer was 20000.

(2)
Example 1
In a 50 ml stainless steel autoclave containing a magnetic rotor, 0.5 g (2.6 mmol) of the ring-opening metathesis polymer of 5-norbornene-2,3-bischloromethyl obtained in Synthesis Example 3 and 1,1,2-trichloroethane 10 ml was charged and dissolved with stirring at room temperature. To this solution, 0.62 g (12.5 mmol) of hydrazine monohydrate and 5-ethyl-3,7,8-trimethyl-10- (2 ′, 4 ′: 3 ′, 5 ′) synthesized in Synthesis Example 1 were added. -Di-o-methyleneribityl) isoalloxazinium perchlorate (3.4 mg / 6.6 μmol) was added, air was pressurized to 0.2 MPaG, immersed in an oil bath heated to 120 ° C., and stirred for 4 hours. In addition, air exchange was performed once at 2 hours of reaction. After completion of the reaction, the reaction solution was cooled to room temperature, and the reaction solution was poured into 100 ml of methanol to precipitate a polymer. After filtration, the recovered polymer was dried in a vacuum dryer at 40 ° C. for 4 hours to obtain 0.49 g of polymer (recovery rate 98%).

The hydrogenation rate was calculated | required from the < ¹ > H-NMR spectrum analysis of the obtained polymer. The results are shown in Table 1.

Example 2
The polymer was recovered in the same manner as in Example 1 except that 1.24 g (25 mmol) of hydrazine monohydrate was used instead of 0.62 g (12.5 mmol) of hydrazine monohydrate. The hydrogenation rate was calculated | required from the < ¹ > H-NMR spectrum analysis of the obtained polymer. The results are shown in Table 1.

Example 3
5-ethyl-3,7,8-trimethyl-10- (2 ′, 4 ′: 3 ′, 5′-di-o-methyleneribityl) isoalloxazinium perchlorate (3.4 mg / 6.6 μmol) as catalyst Instead of 5-ethyl-3,7,8,10-tetramethylisoalloxazinium perchlorate (2.6 mg / 6.6 μmol) obtained in Synthesis Example 2, it was the same as Example 1. To recover the polymer. The hydrogenation rate was calculated | required from the < ¹ > H-NMR spectrum analysis of the obtained polymer. The results are shown in Table 1.

Example 4
Instead of 0.5 g (2.6 mmol) of a ring-opening metathesis polymer of 5-norbornene-2,3-bischloromethyl as halogen-containing unsaturated polyolefin, chloroprene rubber (trade name Skyprene manufactured by Tosoh Corporation) 0 The polymer was recovered in the same manner as in Example 1 except that 0.23 g (2.6 mmol) was used. The hydrogenation rate was calculated | required from the < ¹ > H-NMR spectrum analysis of the obtained polymer. The results are shown in Table 1.

Example 5
Instead of using 0.57 g (2.6 mmol) of the ring-opening metathesis polymer of 5-norbornene-2,3-bischloromethyl as the halogen-containing unsaturated polyolefin, 0.77 g (2.6 mmol) of polychloroprene latex was used. Reacted in the same manner as in Example 1 to recover the polymer. The hydrogenation rate was calculated | required from the < ¹ > H-NMR spectrum analysis of the obtained polymer. The results are shown in Table 1.

Comparative Example 1
In a 50 ml autoclave containing a magnetic rotor, 0.5 g (2.6 mmol) of the ring-opening metathesis polymer of 5-norbornene-2,3-bischloromethyl obtained in Synthesis Example 3 and 25 ml of o-dichlorobenzene, As a catalyst, 0.1 g of 5% Pd / activated carbon was charged and stirred at a hydrogen pressure of 1 MPaG and 150 ° C. for 4 hours. After completion of the reaction, the reaction solution was cooled to room temperature, and then the catalyst was filtered. From the obtained filtrate, o-dichlorobenzene was removed by an evaporator to obtain a crude polymer. The crude polymer was dissolved in 10 g of chloroform and added to 50 g of methanol for reprecipitation purification. The precipitated polymer was filtered and then dried at 40 ° C. for 5 hours in a vacuum dryer. Although the hydrogenation rate was calculated | required from the < ¹ > H-NMR spectrum analysis of the obtained polymer, hydrogenation reaction did not advance. The results are shown in Table 1.

Comparative Example 2
A reaction was carried out in the same manner as in Comparative Example 1 except that 5% Pd / silica was used instead of 5% Pd / activated carbon, and a polymer was recovered. Although the hydrogenation rate was calculated | required from the < ¹ > H-NMR spectrum analysis of the obtained polymer, hydrogenation reaction did not advance. The results are shown in Table 1.

Comparative Example 3
Except for using 5% Pd / alumina instead of 5% Pd / activated carbon, a reaction was carried out in the same manner as in Comparative Example 1 to attempt a hydrogenation reaction. At that time, a dehydrochlorination reaction proceeded. The results are shown in Table 1.

Comparative Example 4
Except for using 5% Ru / alumina instead of 5% Pd / activated carbon, a reaction was carried out in the same manner as in Comparative Example 1 to attempt a hydrogenation reaction. At that time, a dehydrochlorination reaction proceeded. The results are shown in Table 1.

Comparative Example 5
In place of 0.5 g (2.6 mmol) of the ring-opening metathesis polymer of 5-norbornene-2,3-bischloromethyl obtained in Synthesis Example 3, chloroprene rubber (trade name Skyprene manufactured by Tosoh Corporation) 0 A reaction was performed in the same manner as in Comparative Example 1 except that 0.23 g (2.6 mmol) was used, and the polymer was recovered. Although the hydrogenation rate was calculated | required from the < ¹ > H-NMR spectrum analysis of the obtained polymer, hydrogenation reaction did not advance. The results are shown in Table 1.

Claims (3)

Production of a halogen-containing saturated polyolefin characterized by hydrogenating a halogen-containing unsaturated polyolefin using a flavin compound represented by the following general formula (1) as a hydrogenation catalyst in the presence of an organic solvent, hydrazine and oxygen Method.

(1)
(Wherein R ₁ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a phenylalkyl group having 7 to 12 carbon atoms, and R ₂ and R ₃ are each independently a hydrogen atom, 1 to 1 carbon atom) 10 represents an alkyl group or an alkoxy group, R ₄ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group, a 2,4: 3,5-di-o-methyleneribityl group, or a phenyl group; R ₅ represents an alkyl group having 1 to 10 carbon atoms and a phenylalkyl group having 7 to 12 carbon atoms.) The flavin-based compound is 5-ethyl-3,7,8-trimethyl-10- (2 ′, 4 ′: 3 ′, 5′-di-o-methyleneribityl) isoalloxazinium perchlorate and / or 5-ethyl. The process for producing a halogen-containing saturated polyolefin according to claim 1, wherein the process is -3,7,8,10-tetramethylisoalloxazinium perchlorate. The method for producing a halogen-containing saturated polyolefin according to claim 1 or 2, wherein the halogen-containing unsaturated polyolefin is a 5-norbornene-2,3-bischloromethyl ring-opening metathesis polymer and / or polychloroprene. .