JP2016037511A - 1,2-polybutadienediol hydride and method for producing and purifying the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide: a 1,2-polybutadienediol hydride having a small content of 1,12-dodecanediol; a method for producing the same; and a method for purifying the same.SOLUTION: There can be obtained a 1,2-polybutadienediol hydride having a small content of 1,12-dodecanediol by a method for producing a 1,2-polybutadienediol hydride which comprises a step of treating an organic solvent solution during hydrogenation reaction or after hydrogenation reaction with an adsorbent when 1,2-polybutadienediol is hydrogenated in the presence of an organic solvent and a hydrogenation catalyst.SELECTED DRAWING: None

Description

  The present invention relates to a high purity 1,2-polybutadiene diol hydride. The present invention also relates to a method for producing or purifying 1,2-polybutadienediol hydride.

  Hydrogenation of 1,2-polybutadienediol can be obtained by hydrogenating 1,2-polybutadienediol in the presence of an organic solvent and a hydrogenation catalyst (Patent Document 1, Patent Document 2, Patent Document 3). The obtained 1,2-polybutadienediol hydride contains 1,12-dodecanediol as an impurity. 1,12-dodecanediol may precipitate in 1,2-polybutadienediol hydride at low temperatures (Patent Document 4). Therefore, particularly in applications where the material is required to be transparent, a 1,2-polybutadienediol hydride having a low 1,12-dodecanediol content has been required.

  In Patent Document 4, in the method for producing 1,2-polybutanediol hydride by hydrogenation reaction from 1,2-polybutadienediol, the 1,2-polybutadienediol hydride obtained after the hydrogenation reaction is reduced in pressure. It is described that 1,2-polybutadienediol hydride having a 1,12-dodecanediol content of 1490 ppm can be obtained by thin-film distillation.

JP 7-247302 A JP 7-247303 A Japanese Patent Application Laid-Open No. 9-100371 JP 2004-263036 A

  An object of the present invention is to provide a 1,2-polybutadienediol hydride having a low content of 1,12-dodecanediol. Another object of the present invention is to provide a method for producing a 1,2-polybutadienediol hydride having a low content of 1,12-dodecanediol. Another object of the present invention is to provide a method for purifying a 1,2-polybutadienediol hydride containing 1,12-dodecanediol.

  The present inventors have made extensive studies to solve the above problems. As a result, it was found that the use of a certain kind of adsorbent can reduce the content of 1,12-dodecanediol in 1,2-polybutadienediol hydride by an industrially simple method. In particular, the inventors have found a 1,2-polybutadienediol hydride having a content of 1,12-dodecanediol of 1000 ppm or less and a method for producing the same. Moreover, the refinement | purification method of the 1, 2- polybutadienediol hydride containing 1,12-dodecanediol was discovered. The present invention has been completed based on these findings.

That is, the present invention
(1) 1,2-polybutadienediol hydride in which the content of 1,12-dodecanediol is 1000 ppm or less, (2) The content of 1,12-dodecanediol is in the range of 0.1 ppm to 1000 ppm (1) 1,2-polybutadiene diol hydride according to (1), (1) or (2), wherein the number average molecular weight (Mn) is 300 to 10,000, (4) molecular weight The 1,2-polybutadiene diol hydride according to any one of (1) to (3), wherein the distribution (Mw / Mn) is 1.01 to 2.50.
In addition, (5) when hydrogenating 1,2-polybutadiene diol in the presence of an organic solvent and a hydrogenation catalyst, the organic solvent solution is treated with an adsorbent during or after the hydrogenation reaction. 1,2-polybutadienediol hydride, (6) 1,2-polybutadienediol hydrogen according to (5), wherein the content of 1,12-dodecanediol in 1,2-polybutadienediol hydride is 3000 ppm or less (7) The production method according to (5) or (6), wherein the step of treating with an adsorbent is a step of adding and mixing the adsorbent to a solution during or after the hydrogenation reaction. (8) 0.1 to 20% by mass of an adsorbent is added to the total amount of 1,2-polybutadienediol and 1,2-polybutadienediol hydride (7 (9) The production method according to any one of (5) to (8), wherein the adsorbent is at least one selected from the group consisting of activated clay, silica gel, activated alumina, and activated carbon. (10) The method according to any one of (5) to (9), wherein the organic solvent is a hydrocarbon solvent.
(11) A method for purifying a 1,2-polybutadienediol hydride comprising a step of contacting an organic solvent solution of 1,2-polybutadienediol hydride containing 1,12-dodecanediol with an adsorbent, (12) The method for purifying 1,2-polybutadienediol hydride according to (11), wherein the 1,2-polybutadienediol hydride after purification has a 1,12-dodecanediol content of 3000 ppm or less, (13) 1,2- The purification method according to (11) or (12), wherein 0.1 to 20% by mass of an adsorbent is added to the amount of polybutadienediol hydride, (14) the adsorbent is activated clay, silica gel, activated alumina, The purification method according to any one of (11) to (13), which is at least one selected from the group consisting of activated carbon, and (15) an organic solvent A hydrocarbon solvent (11) to (14) Purification method according to any one of claims, relates.

  According to the present invention, a 1,2-polybutadienediol hydride having a low content of 1,12-dodecanediol can be easily obtained industrially. In particular, the content of 1,12-dodecanediol in the 1,2-polybutadienediol hydride can be 1000 ppm or less.

Hereinafter, the present invention will be described in detail.
(1,2-Polybutadienediol hydride)
The content of 1,12-dodecanediol (formula (1)) (hereinafter sometimes referred to as DDG) in the 1,2-polybutadienediol hydride of the present invention is 1000 ppm or less, preferably 800 ppm or less, more preferably. Is 500 ppm or less, more preferably 300 ppm or less. By setting the DDG content in the 1,2-polybutadienediol hydride to 1000 ppm or less, precipitation of DDG can be suppressed even under low temperature conditions. Although the minimum of DDG content is not specifically limited, It is 0.1 ppm or more.

  The content of 1,12-dodecanediol in 1,2-polybutadienediol hydride can be measured by an internal standard method in which a capillary column is attached to a gas chromatograph.

  In the present invention, 1,2-polybutadiene diol refers to a polymer in which both ends of a polymer chain obtained by polymerizing butadiene are modified with hydroxyl groups. 1,2-polybutadienediol has a ratio of 1,2-bond units (formula (2)) and 1,4-bond units (formula (3)) constituting the main chain of 50:50 to 98: 2. Yes, preferably 70:30 to 98: 2.

The 1,2-polybutadiene diol hydride of the present invention indicates that the carbon-carbon double bond in 1,2-polybutadiene diol is hydrogenated. The hydrogenation rate (mol%) is not particularly limited, but is preferably 80% or more, more preferably 90% or more, and further preferably 95% or more.
The hydrogenation rate (mol%) is a value defined by the following formula.
Hydrogenation rate (mol%) = (A / B) × 100
Where A is the number of moles of monomer unit units hydrogenated in the 1,2-polybutadienediol hydride, and B is the number of moles of all monomer unit units contained in the 1,2-polybutadienediol hydride. It is. A and B are calculated by the integration ratio of ¹ H-NMR.

  The number average molecular weight (Mn) of the 1,2-polybutadiene hydride of the present invention is preferably 300 to 10,000, more preferably 300 to 5,000 as measured by GPC (gel filtration) method using polystyrene as an index. More preferably, it is 300-4000. The molecular weight distribution (Mw / Mn) is preferably from 1.01 to 3.00, and more preferably from 1.01 to 2.50.

(Method for producing 1,2-polybutadienediol hydride)
1,2-polybutadiene diol as a raw material for production can be obtained by a method in which polybutadiene is prepared by polymerizing butadiene in a solution in the presence of a sodium catalyst, and ethylene oxide is added thereto. Specific examples of commercially available 1,2-polybutadiene diol include NISSO-PB-G-1000 (manufactured by Nippon Soda Co., Ltd.), NISSO-PB-G-2000 (manufactured by Nippon Soda Co., Ltd.), NISSO-PB-G-3000. (Nippon Soda Co., Ltd.). These 1,2-polybutadiene diols contain 4,8-dodecadiene-1,12-diol or the like, which is usually derived from a polymerization reaction of butadiene, as impurities. These are considered to be 1,12-dodecanediol by the hydrogenation reaction.

  The reaction for hydrogenating 1,2-polybutadiene diol is not particularly limited as long as hydrogenation is performed in the presence of an organic solvent and a hydrogenation catalyst. For example, Patent Document 1, Patent Document 2, Patent Document 3 and the like have been described. It can be performed by a known method.

  As the organic solvent used for the hydrogenation reaction, conventionally used various organic solvents are used. Examples of the organic solvent include hydrocarbon solvents such as hexane, heptane, octane, nonane, decane, cyclohexane, methylcyclohexane, isoparaffin, benzene, toluene, xylene, trimethylbenzene, and solvent naphtha; n-propyl alcohol, isopropyl alcohol, n -Alcohol solvents such as butyl alcohol; ethers such as diethyl ether, dipropyl ether and tetrahydrofuran; ester solvents such as ethyl acetate and butyl acetate; or a mixed solvent composed of any combination thereof. However, it is not limited to those exemplified. Of these, hydrocarbon solvents such as hexane, heptane, octane, nonane, decane, cyclohexane, methylcyclohexane, normal paraffin, isoparaffin, benzene, toluene, xylene, trimethylbenzene, and solvent naphtha are preferable, octane, normal paraffin, and isoparaffin. It is more preferable that

  Although the usage-amount of an organic solvent is not specifically limited, Preferably it is 30-300 mass parts with respect to 100 mass parts of 1, 2- polybutadienediol.

  The hydrogenation catalyst used for the hydrogenation reaction is not particularly limited as long as it is a catalyst for smoothly performing the hydrogenation reaction. Examples of the hydrogenation catalyst that can be used in the present invention include nickel-based catalysts, cobalt-based catalysts, ruthenium-based catalysts, rhodium-based catalysts, palladium-based catalysts, platinum-based catalysts, and mixtures or alloy-based catalysts thereof. Of these, nickel-based catalysts and ruthenium-based catalysts are preferable from the viewpoint that hydroxyl group hydrogenolysis hardly occurs.

  These hydrogenation catalysts can be used alone, as a solid or soluble homogeneous complex, or as a carrier-supported type supported on a carrier such as carbon, silica, or diatomaceous earth. Of these, a catalyst supported on a diatomaceous earth support is preferred. Further, as the hydrogenation catalyst, in addition to the above metal catalyst, a metal complex obtained by reducing a compound containing nickel, titanium, cobalt and the like with an organometallic compound (for example, trialkylaluminum, alkyllithium, etc.) can also be used.

  The amount of the hydrogenation catalyst used varies depending on the type of metal and the amount supported, but is preferably 0.01 to 20% by mass with respect to 1,2-polybutadiene diol. The hydrogenation catalyst may be attached to the reactor as a fixed bed or suspended in the reaction solvent.

  The hydrogen to be used is not particularly limited as long as it does not contain a component that becomes a catalyst poison.

The production method of the present invention includes a step of treating an organic solvent solution during or after the hydrogenation reaction with an adsorbent when hydrogenating 1,2-polybutadienediol. The step of treating with the adsorbent is not particularly limited as long as it is a step of bringing the adsorbent into contact with 1,12-dodecanediol. Specifically, the organic solvent solution is preferably passed through a column packed with an adsorbent, or the adsorbent is added to and mixed with the organic solvent solution during or after the hydrogenation reaction. More preferably, the adsorbent is added to and mixed with the organic solvent solution after the addition reaction.
In addition, the step of adding and mixing the adsorbent to the organic solvent solution during the hydrogenation reaction may be performed as long as the adsorbent is added to the hydrogenation reaction system. May be added from the beginning, or may be added during the hydrogenation reaction. In addition, when the hydrogenation reaction is performed in multiple stages, it may be added in any one of the stages.

  The adsorbent is not particularly limited as long as it can adsorb and remove 1,12-dodecanediol. Specific examples include activated clay, silica gel, activated alumina, and activated carbon, and these can also be used in combination.

The addition amount of the adsorbent may be appropriately selected depending on the desired quality, but is preferably 0.1 to 20% by mass with respect to the total amount of 1,2-polybutadienediol and 1,2-polybutadienediol hydride, More preferably, it is 1-20 mass%, More preferably, it is 5-20 mass%.
When the content of 1,12-dodecanediol can be assumed, the amount of adsorbent added may be 0.25 to 50 times the amount of adsorbent with respect to 1,12-dodecanediol. It is more preferably 5 to 30 times, and further preferably 5 to 30 times the amount.

  The temperature at which the adsorbent is added and mixed is not particularly limited, but is preferably 10 ° C to 100 ° C, more preferably 30 ° C to 80 ° C, and 40 ° C to 80 ° C. Further preferred.

(Purification method of 1,2-polybutadienediol hydride)
The purification method of the present invention is a method for purifying a 1,2-polybutadienediol hydride comprising a step of bringing an organic solvent solution of 1,2-polybutadienediol hydride containing 1,12-dodecanediol into contact with an adsorbent. An organic solvent solution of 1,2-polybutadienediol hydride containing 1,12-dodecanediol is prepared by mixing 1,2-polybutadienediol hydride containing 1,12-dodecanediol and an organic solvent. can do.

  The organic solvent is not particularly limited as long as it is an organic solvent in which 1,2-polybutadienediol hydride is dissolved. Specifically, hydrocarbon solvents such as hexane, heptane, octane, nonane, decane, cyclohexane, methylcyclohexane, normal paraffin, isoparaffin, benzene, toluene, xylene, trimethylbenzene, solvent naphtha; n-propyl alcohol, isopropyl alcohol And alcohol solvents such as n-butyl alcohol; ether solvents such as diethyl ether, dipropyl ether and tetrahydrofuran; ester solvents such as ethyl acetate and butyl acetate; or mixed solvents composed of any combination thereof. However, it is not limited to those exemplified. Of these, hydrocarbon solvents such as hexane, heptane, octane, nonane, decane, cyclohexane, methylcyclohexane, normal paraffin, isoparaffin, benzene, toluene, xylene, trimethylbenzene, and solvent naphtha are preferable, and among them, octane and normal paraffin Isoparaffin is more preferable.

  The amount of the organic solvent mixed is not particularly limited, but is preferably 30 to 300 parts by mass with respect to 100 parts by mass of 1,2-polybutadienediol hydride.

  The purification method of the present invention includes a step of bringing an organic solvent solution of 1,2-polybutadienediol hydride containing 1,12-dodecanediol into contact with an adsorbent, and the adsorbent and 1,12-dodecanediol. There is no particular limitation as long as it is a step of contacting. Specifically, it is preferably a step of adding an adsorbent to an organic solvent solution of 1,2-polybutadienediol hydride containing 1,12-dodecanediol and mixing.

  The adsorbent is not particularly limited as long as it can adsorb and remove 1,12-dodecanediol. Specific examples include activated clay, silica gel, activated alumina, and activated carbon, and these can also be used in combination.

The addition amount of the adsorbent may be appropriately selected depending on the desired quality, but is preferably 0.1 to 20% by mass, more preferably 1 to 20% by mass with respect to the amount of 1,2-polybutadienediol hydride. %, More preferably 5 to 20% by mass.
When the content of 1,12-dodecanediol can be assumed, the amount of adsorbent added may be 0.25 to 50 times the amount of adsorbent with respect to the content of 1,12-dodecanediol. , 0.5 to 30 times, more preferably 5 to 30 times the amount.

  The temperature at which the adsorbent is added and mixed is not particularly limited, but is preferably 10 ° C to 100 ° C, more preferably 30 ° C to 80 ° C, and 40 ° C to 80 ° C. Further preferred.

  Hereinafter, the present invention will be described more specifically with reference to examples. It should be noted that the present invention is not limited by the following examples, and can of course be implemented with appropriate modifications within a range that can be adapted to the spirit of the present invention. To be included in the scope.

Next, an Example and a comparative example are shown and this invention is demonstrated in detail. The present invention is not limited to the following examples.
The content of 1,12-dodecanediol in 1,2-polybutadienediol hydride was measured by an internal standard method in which a capillary column was attached to a gas chromatograph. The measurement conditions are shown below.
Analysis method: Internal standard method (using naphthalene as internal standard)
Gas chromatography analyzer (GC): Shimadzu GC-2014
Column: Agilent J & W DB-624 (60 m × 0.32 mm ID, 1.8 μm)
Detector: FID
Inlet temperature: 250 ° C
Detector temperature: 250 ° C
Column temperature: 50 ° C. → 25 ° C./min→250° C./28 min Carrier gas: Helium split ratio: 1:30

[Synthesis Example 1]
In an autoclave having a capacity of 0.98 liter equipped with a heater for heating, a stirrer and a thermometer, 12.01 g of a diatomaceous earth-supported nickel catalyst was charged and purged with nitrogen. To this was added 250 g of a 60 mass% octane solution of 1,2-polybutadienediol (“G-1000” manufactured by Nippon Soda Co., Ltd., number average molecular weight (Mn): 1400). Hydrogen gas was pressurized and sealed in the autoclave until the pressure became 2.0 MPa. The hydrogenation reaction was carried out until the hydrogenation rate reached 84% while maintaining the temperature at 120 to 130 ° C. Subsequently, after the temperature in the autoclave was raised to 165 ° C., hydrogen gas was pressurized and sealed until the hydrogen pressure in the autoclave reached 9.2 MPa. The hydrogenation reaction was carried out for 3 hours while maintaining the temperature at 165 ° C. After the autoclave was cooled to room temperature, the reaction solution was filtered to remove the hydrogenation catalyst. Octane was added to the filtrate to prepare an octane solution having a 1,2-polybutadienediol hydride concentration of 50% by mass (solution A). The obtained 1,2-polybutadienediol hydride had a hydrogenation rate of 99%, an iodine value of 13.8 Ig / 100 g, and a hydroxyl value of 64.3 KOHmg / g.

(Hydroxyl value)
This is the number of mg of potassium hydroxide required to acetylate the OH group contained in 1 g of the sample. It measured by the method based on JISK0070: 1992.
(Iodine number)
This is a value obtained by converting the amount of halogen that reacts with 100 grams of the sample into grams of iodine. It measured by the method based on JISK0070: 1992.

[Comparative Example 1]
When one sheet of filter paper (production filter paper (No. 28)) was set on the pressure filter, a suspension of 1.25 g of Radiolite (# 200) in 50 mL of octane was precoated. After heating the pressure filter to 80 ° C., 50 g of Solution A was added. Filtration was performed under a nitrogen pressure of 0.2 MPa to obtain a filtrate. The solvent was removed by concentration under reduced pressure to obtain 1,2-polybutadienediol hydride. The obtained 1,2-polybutadienediol hydride had a DDG content of 4080 ppm.

[Example 1]
50 g of the solution A prepared in Synthesis Example 1 and 0.5 g of activated clay (manufactured by Wako Pure Chemical Industries, Ltd.) were added to a 100 mL four-necked flask equipped with a condenser, a stirring blade and a thermometer. The mixture was stirred at 80 ° C. for 1 hour to obtain a mixed solution 1.
When one sheet of filter paper (production filter paper (No. 28)) was set on the pressure filter, a suspension of 1.25 g of Radiolite (# 200) in 50 mL of octane was precoated. After heating the pressure filter to 80 ° C., the mixed solution 1 was added. Filtration was performed under a nitrogen pressure of 0.2 MPa to obtain a filtrate. The solvent was removed by concentration under reduced pressure to obtain 1,2-polybutadienediol hydride. The obtained 1,2-polybutadienediol hydride had a DDG content of 3320 ppm.

[Example 2]
50 g of the solution A prepared in Synthesis Example 1 and 1.5 g of activated clay (manufactured by Wako Pure Chemical Industries, Ltd.) were added to a 100 mL four-necked flask equipped with a condenser, a stirring blade and a thermometer. The mixture was stirred at 80 ° C. for 1 hour to obtain a mixed solution 2.
When one sheet of filter paper (production filter paper (No. 28)) was set on the pressure filter, a suspension of 1.25 g of Radiolite (# 200) in 50 mL of octane was precoated. After heating the pressure filter to 80 ° C., the mixture 2 was added. Filtration was performed under a nitrogen pressure of 0.2 MPa to obtain a filtrate. The solvent was removed by concentration under reduced pressure to obtain 1,2-polybutadienediol hydride. The resulting 1,2-polybutadienediol hydride had a DDG content of 2450 ppm.

[Example 3]
50 g of the solution A prepared in Synthesis Example 1 and 0.25 g of activated carbon (manufactured by Wako Pure Chemical Industries, Ltd. (dry powder product)) were added to a 100 mL four-necked flask equipped with a condenser, a stirring blade and a thermometer. The mixture was stirred at 80 ° C. for 1 hour to obtain a mixed solution 3.
When one sheet of filter paper (production filter paper (No. 28)) was set on the pressure filter, a suspension of 1.25 g of Radiolite (# 200) in 50 mL of octane was precoated. After heating the pressure filter to 80 ° C., the mixture 3 was added. Filtration was performed under a nitrogen pressure of 0.2 MPa to obtain a filtrate. The solvent was removed by concentration under reduced pressure to obtain 1,2-polybutadienediol hydride. The obtained 1,2-polybutadienediol hydride had a DDG content of 3250 ppm.

[Example 4]
50 g of the solution A prepared in Synthesis Example 1 and 0.25 g of activated carbon (manufactured by Wako Pure Chemical Industries, Ltd. (dry powder product)) were added to a 100 mL four-necked flask equipped with a condenser, a stirring blade and a thermometer. The mixture was stirred at 40 ° C. for 1 hour to obtain a mixed solution 4.
When one sheet of filter paper (production filter paper (No. 28)) was set on the pressure filter, a suspension of 1.25 g of Radiolite (# 200) in 50 mL of octane was precoated. After heating the pressure filter to 40 ° C., the mixture 4 was added. Filtration was performed under a nitrogen pressure of 0.2 MPa to obtain a filtrate. The solvent was removed by concentration under reduced pressure to obtain 1,2-polybutadienediol hydride. The obtained 1,2-polybutadienediol hydride had a DDG content of 3000 ppm.

[Example 5]
50 g of the solution A prepared in Synthesis Example 1 and 0.5 g of activated carbon (manufactured by Wako Pure Chemical Industries, Ltd. (dry powder product)) were added to a 100 mL four-necked flask equipped with a condenser, a stirring blade and a thermometer. The mixture was stirred at 80 ° C. for 1 hour to obtain a mixed solution 5.
When one sheet of filter paper (production filter paper (No. 28)) was set on the pressure filter, a suspension of 1.25 g of Radiolite (# 200) in 50 mL of octane was precoated. After heating the pressure filter to 80 ° C., the mixed solution 5 was added. Filtration was performed under a nitrogen pressure of 0.2 MPa to obtain a filtrate. The solvent was removed by concentration under reduced pressure to obtain 1,2-polybutadienediol hydride. The obtained 1,2-polybutadienediol hydride had a DDG content of 2670 ppm.

[Example 6]
50 g of the solution A prepared in Synthesis Example 1 and 1.5 g of activated carbon (manufactured by Wako Pure Chemical Industries, Ltd. (dry powder product)) were added to a 100 mL four-necked flask equipped with a condenser, a stirring blade, and a thermometer. It stirred at 80 degreeC for 1 hour, and the liquid mixture 6 was obtained.
When one sheet of filter paper (production filter paper (No. 28)) was set on the pressure filter, a suspension of 1.25 g of Radiolite (# 200) in 50 mL of octane was precoated. After heating the pressure filter to 80 ° C., the mixed solution 6 was added. Filtration was performed under a nitrogen pressure of 0.2 MPa to obtain a filtrate. The solvent was removed by concentration under reduced pressure to obtain 1,2-polybutadienediol hydride. The obtained 1,2-polybutadienediol hydride had a DDG content of 1620 ppm.

[Example 7]
50 g of the solution A prepared in Synthesis Example 1 and 2.5 g of activated carbon (manufactured by Wako Pure Chemical Industries, Ltd. (dry product)) were added to a 100 mL four-necked flask equipped with a condenser, a stirring blade and a thermometer. The mixture was stirred at 80 ° C. for 1 hour to obtain a mixed solution 7.
When one sheet of filter paper (production filter paper (No. 28)) was set on the pressure filter, a suspension of 1.25 g of Radiolite (# 200) in 50 mL of octane was precoated. After heating the pressure filter to 80 ° C., the mixed solution 7 was added. Filtration was performed under a nitrogen pressure of 0.2 MPa to obtain a filtrate. The solvent was removed by concentration under reduced pressure to obtain 1,2-polybutadienediol hydride. The DDG content of the obtained 1,2-polybutadienediol hydride was 300 ppm or less (below the lower limit of quantification).

[Example 8]
Add 50 g of solution A prepared in Synthesis Example 1 and 1.0 g of activated carbon (K-W50 (50% water-containing product)) to a 100 mL four-necked flask equipped with a condenser, stirring blade and thermometer. did. The mixture was stirred at 80 ° C. for 1 hour to obtain a liquid mixture 8.
When one sheet of filter paper (production filter paper (No. 28)) was set on the pressure filter, a suspension of 1.25 g of Radiolite (# 200) in 50 mL of octane was precoated. After heating the pressure filter to 80 ° C., the liquid mixture 8 was added. Filtration was performed under a nitrogen pressure of 0.2 MPa to obtain a filtrate. The solvent was removed by concentration under reduced pressure to obtain 1,2-polybutadienediol hydride. The obtained 1,2-polybutadienediol hydride had a DDG content of 2910 ppm.

[Example 9]
Add 50 g of solution A prepared in Synthesis Example 1 and 1.0 g of activated carbon (Y-W50 (50% water-containing product) by Futamura Chemical Co., Ltd.) to a 100 mL four-necked flask equipped with a condenser, stirring blade and thermometer. did. The mixture was stirred at 80 ° C. for 1 hour to obtain a mixed solution 9.
When one sheet of filter paper (production filter paper (No. 28)) was set on the pressure filter, a suspension of 1.25 g of Radiolite (# 200) in 50 mL of octane was precoated. After heating the pressure filter to 80 ° C., the mixed solution 9 was added. Filtration was performed under a nitrogen pressure of 0.2 MPa to obtain a filtrate. The solvent was removed by concentration under reduced pressure to obtain 1,2-polybutadienediol hydride. The obtained 1,2-polybutadienediol hydride had a DDG content of 2840 ppm.

[Example 10]
50 g of Solution A prepared in Synthesis Example 1 and 0.5 g of silica gel (Wako Pure Chemical Industries, Ltd. (Wakogel C-300)) were added to a 100 mL four-necked flask equipped with a condenser, a stirring blade and a thermometer. . The mixture was stirred at 80 ° C. for 1 hour to obtain a mixed solution 10.
When one sheet of filter paper (production filter paper (No. 28)) was set on the pressure filter, a suspension of 1.25 g of Radiolite (# 200) in 50 mL of octane was precoated. After heating the pressure filter to 80 ° C., the mixed solution 10 was added. Filtration was performed under a nitrogen pressure of 0.2 MPa to obtain a filtrate. The solvent was removed by concentration under reduced pressure to obtain 1,2-polybutadienediol hydride. The obtained 1,2-polybutadienediol hydride had a DDG content of 3200 ppm.

[Example 11]
50 g of the solution A prepared in Synthesis Example 1 and 0.5 g of activated alumina (manufactured by Wako Pure Chemical Industries, Ltd.) were added to a 100 mL four-necked flask equipped with a condenser, a stirring blade and a thermometer. The mixture was stirred at 80 ° C. for 1 hour to obtain a mixed solution 11.
When one sheet of filter paper (production filter paper (No. 28)) was set on the pressure filter, a suspension of 1.25 g of Radiolite (# 200) in 50 mL of octane was precoated. After heating the pressure filter to 80 ° C., the mixture 11 was added. Filtration was performed under a nitrogen pressure of 0.2 MPa to obtain a filtrate. The solvent was removed by concentration under reduced pressure to obtain 1,2-polybutadienediol hydride. The obtained 1,2-polybutadienediol hydride had a DDG content of 3550 ppm.

Claims (15)

A 1,2-polybutadienediol hydride having a content of 1,12-dodecanediol of 1000 ppm or less. The 1,2-polybutadienediol hydride according to claim 1, wherein the content of 1,12-dodecanediol is 0.1 ppm or more and 1000 ppm or less. The 1,2-polybutadienediol hydride according to claim 1 or 2, having a number average molecular weight (Mn) of 300 to 10,000. Molecular weight distribution (Mw / Mn) is 1.01-2.50, The 1, 2- polybutadienediol hydride of any one of Claims 1-3. 1,2-polybutadiene diol comprising a step of treating an organic solvent solution during or after hydrogenation with an adsorbent when hydrogenating 1,2-polybutadiene diol in the presence of an organic solvent and a hydrogenation catalyst A method for producing a hydride. The method for producing a 1,2-polybutadienediol hydride according to claim 5, wherein the content of 1,12-dodecanediol in the 1,2-polybutadienediol hydride is 3000 ppm or less. The manufacturing method according to claim 5 or 6, wherein the step of treating with an adsorbent is a step of adding and mixing the adsorbent to a solution during or after the hydrogenation reaction. The production method according to claim 7, wherein an adsorbent is added in an amount of 0.1 to 20% by mass based on the total amount of 1,2-polybutadiene diol and 1,2-polybutadiene diol hydride. The production method according to any one of claims 5 to 8, wherein the adsorbent is at least one selected from the group consisting of activated clay, silica gel, activated alumina, and activated carbon. The production method according to any one of claims 5 to 9, wherein the organic solvent is a hydrocarbon solvent. A method for purifying a 1,2-polybutadienediol hydride comprising a step of contacting an organic solvent solution of a 1,2-polybutadienediol hydride containing 1,12-dodecanediol with an adsorbent. The method for purifying 1,2-polybutadienediol hydride according to claim 11, wherein the 1,2-polybutadienediol hydride after purification has a content of 1,12-dodecanediol of 3000 ppm or less. The purification method according to claim 11 or 12, wherein an adsorbent is added in an amount of 0.1 to 20% by mass based on the amount of 1,2-polybutadienediol hydride. The purification method according to any one of claims 11 to 13, wherein the adsorbent is at least one selected from the group consisting of activated clay, silica gel, activated alumina, and activated carbon. The purification method according to any one of claims 11 to 14, wherein the organic solvent is a hydrocarbon solvent.