WO2013076968A1 - β-メルカプトカルボン酸の製造方法 - Google Patents
β-メルカプトカルボン酸の製造方法 Download PDFInfo
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- WO2013076968A1 WO2013076968A1 PCT/JP2012/007451 JP2012007451W WO2013076968A1 WO 2013076968 A1 WO2013076968 A1 WO 2013076968A1 JP 2012007451 W JP2012007451 W JP 2012007451W WO 2013076968 A1 WO2013076968 A1 WO 2013076968A1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/02—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of thiols
- C07C319/04—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of thiols by addition of hydrogen sulfide or its salts to unsaturated compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B61/00—Other general methods
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/26—Separation; Purification; Stabilisation; Use of additives
- C07C319/28—Separation; Purification
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
- C07C323/50—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton
- C07C323/51—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton
- C07C323/52—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being acyclic and saturated
Definitions
- the present invention relates to a method for producing ⁇ -mercaptocarboxylic acid using an unsaturated carboxylic acid.
- ⁇ -mercaptocarboxylic acid is a useful compound as a raw material for organic synthetic products such as agricultural chemicals and pharmaceuticals, and as a raw material for vinyl chloride stabilizers, crosslinking agents for epoxy resins and acrylate polymers, and plastic lens monomers. is there.
- Examples of the method for producing ⁇ -mercaptocarboxylic acid include the following.
- Patent Document 1 discloses a method in which acrylic acid and thiosulfate are reacted in an aqueous medium to form Bunte salt as a precursor of ⁇ -mercaptopropionic acid, and then this Bunte salt is hydrolyzed in the presence of an acid. Is described.
- Patent Document 2 describes a method in which an alkali acrylate aqueous solution is added to an aqueous solution of an alkali hydrosulfide in the presence of an alkali hydroxide to react, neutralize with an acid, and further reduce with zinc. .
- Patent Document 3 in a method of reacting an unsaturated carboxylic acid and a hydrogen sulfide and acidifying the obtained reaction medium to obtain a mercaptocarboxylic acid, other than hydrogen sulfide supplied by neutralization of the unsaturated carboxylic acid.
- hydrogen sulfide and the reaction is carried out under a pressure of at least 8 bar. Further, it is described that the hydrogen sulfide is obtained by reaction of H 2 S with sodium hydroxide or the like.
- Patent Document 4 discloses a process for producing ⁇ -mercaptocarboxylic acid by reacting ⁇ -unsaturated carboxylic acid and hydrogen sulfide in an aqueous solution in the presence of a basic compound, and the above reaction is carried out in 3.5 to It describes that it is performed under a pressure condition of 20.0 MPaG.
- Patent Document 5 describes that sulfur is used when an unsaturated nitrile is added to an alkali hydrosulfide aqueous solution to react, neutralize and hydrolyze to produce mercaptocarboxylic acid.
- Patent Document 3 or 4 since the reaction is performed under pressure, it is necessary to maintain the pressure state, and the manufacturing process and the like are complicated. In addition, it is necessary to separately provide a manufacturing facility and a pressure device for pressurization, which increases the burden of manufacturing costs.
- Comparative Example 1 of Patent Document 4 an example in which the reaction was performed at normal pressure was described, but there was room for improvement in the reaction yield.
- R 1 and R 2 each represent hydrogen or a C1-C4 alkyl group, which may be the same or different.
- X is the formula:. Is synonymous with alkali hydroxide represented by XOH) reaction solution containing the compound represented by the Obtaining a step; Neutralizing the reaction solution obtained in the step with an acid, The amount of the alkali hydroxide is not less than the total number of moles of the unsaturated carboxylic acid and the hydrogen sulfide, and is represented by the following general formula (3)
- Under normal pressure includes a state of slight pressure generated when hydrogen sulfide is blown, and is in a range of about 0.09 to 0.13 MPa.
- mercaptocarboxylic acid can be obtained in high yield under normal pressure. Moreover, by using hydrogen sulfide as a raw material, the by-product of dithiodicarboxylic acid that occurs when neutralizing the reaction solution can be suppressed, and an industrially simple method can be provided.
- the production method of ⁇ -mercaptocarboxylic acid of the present invention has the following steps a and b. Each process is demonstrated in order.
- R 1 and R 2 each represent hydrogen or a C1-C4 alkyl group, and may be the same or different.
- R 1 and R 2 have the same meaning as in the formula (1), and X has the same meaning as the alkali hydroxide represented by the formula: XOH.
- step a the amount of alkali hydroxide is not less than the total number of moles of unsaturated carboxylic acid and hydrogen sulfide represented by the general formula (1).
- the amount of alkali hydroxide is preferably 1 or more, more preferably 1.5 or more, relative to the total number of moles of unsaturated carboxylic acid and hydrogen sulfide.
- the upper limit is 5 times or less, preferably 4 times or less, more preferably 2.5 times or less, from the viewpoint of increasing the cost when the amount of acid neutralizing the reaction solution increases after completion of the reaction. These upper limit value and lower limit value can be arbitrarily combined.
- step a can be performed by the following method.
- An unsaturated carboxylic acid represented by the general formula (1) is added to an alkali hydroxide aqueous solution to form a salt. Hydrogen sulfide is then blown and reacted with the unsaturated carboxylate. (2) Hydrogen sulfide is blown into an alkali hydroxide aqueous solution, and then an unsaturated carboxylic acid represented by the general formula (1) is added and reacted.
- step a can be performed by the following method (3).
- the amount of alkali hydroxide includes the amount of alkali hydroxide used in advance to produce the unsaturated carboxylic acid alkali salt.
- R 1 and R 2 each independently represent hydrogen or a methyl group, specifically acrylic acid, methacrylic acid, crotonic acid, etc. Can be mentioned. In the case of producing ⁇ -mercaptopropionic acid used for a plastic lens monomer or the like, acrylic acid can be used.
- the alkali hydroxide is represented by the formula: XOH (X represents Na, K), and X is preferably sodium.
- Alkali hydroxide is used as an aqueous solution as described in the above method, but it may be dissolved in a water / alcohol mixed solvent or an alcohol may be added separately. Compared to the conventional method using an organic solvent, it is advantageous in terms of productivity improvement, such as not requiring a solvent recovery step.
- hydrogen sulfide examples include hydrogen sulfide derived from petroleum refining, hydrogen sulfide synthesized by hydrogenating sulfur, and the like.
- step a when hydrogen sulfide is supplied to the alkali hydroxide aqueous solution, it is used as hydrogen sulfide gas.
- it since it is excellent in storage stability, it is usually handled as liquefied hydrogen sulfide.
- the amount of hydrogen sulfide to be added is preferably 1.0 equivalent or more, more preferably 1.5 equivalent or more with respect to the unsaturated carboxylic acid.
- the upper limit is 9.0 equivalents or less, preferably 5.0 equivalents or less, more preferably 3.0 equivalents or less. These upper limit value and lower limit value can be arbitrarily combined.
- Hydrogen sulfide gas can be supplied to the aqueous solution while maintaining the temperature of the aqueous alkali hydroxide solution at 0 to 50 ° C. Thereby, the solubility of hydrogen sulfide gas is improved and the reaction proceeds rapidly.
- the reaction is usually carried out in a temperature range of 20 to 150 ° C., preferably 50 to 140 ° C., more preferably 80 to 130 ° C. Within this temperature range, it is preferable from the viewpoint of reaction rate and reduction in the amount of by-products (dithiodicarboxylic acid and thiodicarboxylic acid) produced.
- the reaction time can be appropriately selected depending on the reaction temperature, but is usually 0.5 to 20 hours, preferably 1 to 15 hours, more preferably 2 to 10 hours, and more preferably 3 to 10 hours.
- step a the reaction can be performed in the presence of sulfur for the purpose of promoting the reaction. Thereby, the reaction of mercaptocarboxylic acid can be completed in a shorter time.
- sulfur is added in an amount of 0.01 to 10 mol%, preferably 0.1 to 5 mol%, more preferably 0.1 to 3 mol% with respect to the unsaturated carboxylic acid.
- the addition method is not particularly limited, but it is preferably present in the aqueous solution when the unsaturated carboxylic acid or the unsaturated carboxylic acid alkali salt is added.
- reaction solution containing the compound represented by the general formula (2) can be obtained.
- the reaction solution contains thiodicarboxylic acid and the like in addition to the compound.
- Step b The reaction solution obtained in step a is neutralized with an acid to obtain ⁇ -mercaptocarboxylic acid represented by the following general formula (3) from the compound represented by the general formula (2).
- R 1 and R 2 have the same meaning as in formula (1).
- mineral acids such as sulfuric acid, hydrochloric acid, nitric acid and phosphoric acid, lower carboxylic acids such as formic acid and acetic acid can be used.
- the acid is used in such an amount that the inside of the reaction system is acidic, and is usually in the range of 0.8 to 1.2 equivalents relative to the alkali hydroxide used in the reaction.
- the addition is preferably carried out while confirming the pH of the reaction solution with a PH meter, and the pH is set to 1 to 3.
- reaction solution containing ⁇ -mercaptocarboxylic acid and thiodicarboxylic acid represented by the general formula (3) can be obtained.
- the reaction solution contains dithiodicarboxylic acid generated from ⁇ -mercaptocarboxylic acid.
- a step of reducing the produced dithiodicarboxylic acid with a metal can be included. This reduction step can be performed after step b (neutralization step) or simultaneously with step b.
- the desired ⁇ -mercaptocarboxylic acid is not immediately obtained from the neutralized reaction mixture, but a reducing agent is added to the solution after completion of the reaction or the reaction solution obtained by neutralization, under acidic conditions.
- the reduction reaction is performed at As a result, dithiodicarboxylic acid as a by-product can be converted into ⁇ -mercaptocarboxylic acid, and the yield can be improved.
- Zinc, iron, tin or the like can be used as the reducing agent metal.
- iron it is preferable to use iron from the viewpoint of economical efficiency and reduction of environmental load.
- these reducing agents may be used individually by 1 type, respectively, or may be used in combination of 2 or more type.
- the amount of the reducing agent used is preferably 1.0 to 5 moles, more preferably 1.2 to 3 moles per mole of dithiodicarboxylic acid by-produced from the viewpoint of yield improvement and economic efficiency. preferable.
- the production method of the present invention produces a small amount of dithiodicarboxylic acid compared to the method of adding NaSH, and can improve the reaction yield of ⁇ -mercaptocarboxylic acid.
- the amount of dithiodicarboxylic acid produced is small, the amount of metal-derived waste used for the reduction can be reduced.
- the aqueous layer is extracted with an organic solvent.
- the organic solvent ethyl acetate, butyl acetate, chloroform, dichloromethane, diethyl ether, isopropyl ether, methyl ethyl ketone, isobutyl ketone and the like are used, and ethyl acetate, butyl acetate and the like are preferably used.
- the target mercaptocarboxylic acid can be obtained by distilling off the organic solvent by concentration under reduced pressure or normal pressure and further purifying by distillation.
- the aqueous solution obtained after extraction is a high-concentration mirabilite or an aqueous inorganic salt solution such as salt, and can be used as, for example, a high-purity mirabilite solution. Further, if crystals are precipitated from a high concentration of mirabilite solution, the deposited crystals can be used as very high purity mirabilite.
- the waste liquid contains almost no organic matter or nitrogen compound, pollution treatment is very simple and economical without affecting the environment.
- the distillation apparatus used for distillation is not particularly limited, and a known distillation apparatus such as a batch distillation apparatus, a continuous distillation apparatus, or a tower type distillation apparatus can be used.
- a continuous rectification apparatus comprising a heater, a rectification column and a condenser from the viewpoint of stabilizing the quality and improving productivity.
- the residue contains by-product thiodicarboxylic acid.
- This distillation residue can be returned to step a again (recycling step).
- the thiodicarboxylic acid contained in the distillation residue can be used as a raw material for ⁇ -mercaptocarboxylic acid.
- it can be heated to impart fluidity, or the distillation residue can be diluted with a solvent, and the distillation residue can be returned to the reaction step for use in the reaction.
- the distillation is completed in a state where 5 to 50%, preferably 10 to 30%, of the distillation residue is left without distilling the whole amount of ⁇ -mercaptocarboxylic acid in the distillation step, and ⁇ -mercaptocarboxylic acid of thiodicarboxylic acid It can also be returned to the reaction step as a solution and subjected to the reaction. By repeating this process, the final yield of ⁇ -mercaptocarboxylic acid can be improved.
- Example 1 A five-necked flask equipped with a stirrer, thermometer, cooling tube, dropping funnel and blowing tube was prepared. After charging 36.3 g (0.88 mol) of 97% sodium hydroxide and 43.3 g of water, uniformly Stir until. While the flask was heated in an oil bath and the internal temperature was maintained at 45 to 50 ° C., 14.4 g (0.20 mol) of acrylic acid was added dropwise from the dropping funnel over 0.5 hours.
- the reaction mass composition after neutralization was 86 mol% for ⁇ -mercaptopropionic acid, 13 mol% for thiodipropionic acid as a by-product, and 0.3 mol% for dithiodipropionic acid.
- 18.0 g of butyl acetate was charged and extraction operation was performed.
- the aqueous layer obtained by liquid separation was further charged with 18.0 g of butyl acetate, and the same extraction operation was performed three times.
- the butyl acetate layers obtained by the extraction three times were combined, and then the butyl acetate was distilled off under reduced pressure using an evaporator.
- the obtained concentrated liquid was charged into a kettle of a distillation apparatus attached to a single tube and distilled under a reduced pressure of 1.2 KPa. Distillation ended when the kettle temperature rose to 150 ° C. The remaining residue was fluid even at 100 ° C. As a main fraction, 17.5 g (0.165 mol) of ⁇ -mercaptopropionic acid having a purity of 99.9% was obtained. The yield based on acrylic acid was 82.5%.
- Example 2 A five-necked flask equipped with a stirrer, thermometer, cooling tube, dropping funnel and blowing tube was prepared. After charging 36.3 g (0.88 mol) of 97% sodium hydroxide and 43.3 g of water, uniformly Stir until. While the flask was heated in an oil bath and the internal temperature was maintained at 45 to 50 ° C., 14.4 g (0.20 mol) of acrylic acid was added dropwise from the dropping funnel over 0.5 hours.
- Example 3 A five-necked flask equipped with a stirrer, thermometer, cooling tube, dropping funnel, and blowing tube was prepared, 36.3 g (0.88 mol) of 97% sodium hydroxide, 43.3 g of water, and 0.072 g (0 .0022 mol) was charged and stirred until uniform. While the flask was heated in an oil bath and the internal temperature was maintained at 45 to 50 ° C., 14.4 g (0.20 mol) of acrylic acid was dropped from the dropping funnel over about 0.5 hours.
- Example 4 A five-necked flask equipped with a stirrer, a thermometer, a cooling tube, a dropping funnel, and a blowing tube was prepared. 47.0 g (1.14 mol) of 97% sodium hydroxide, 54.5 g of water, 0.072 g (0 .0022 mol) was charged and stirred until uniform. While the flask was heated in an oil bath and the internal temperature was maintained at 45 to 50 ° C., 14.4 g (0.20 mol) of acrylic acid was added dropwise from the dropping funnel over 0.5 hours.
- Example 5 The same operation as in Example 1 was performed, and 17.5 g (0.165 mol) of ⁇ -mercaptopropionic acid having a purity of 99.9% was obtained as the main fraction, and 2.8 g ( ⁇ -mercaptopropionic acid 15.7 wt% (0.004 mol), thiodipropionic acid 81.5 wt% (0.012 mol), and dithiodipropionic acid 2.3 wt% (0.0003 mol) were obtained (reaction 1). A five-necked flask equipped with a stirrer, thermometer, cooling tube, dropping funnel and blowing tube was prepared.
- Example 6 Reaction was performed in the same manner as in Example 1 (Reaction 1). Then, using the distillation residue (A) after distillation obtained in Reaction 1, the reaction was carried out under the same conditions as in Example 4 except that the amounts of raw materials to be subjected to the reaction were changed as described in Table 2. Performed (Reaction 2). Similarly, the reaction was performed four times under the same conditions as in Example 4 except that the distillation residue obtained in the previous reaction was used and the amount of raw materials to be subjected to the reaction was changed as described in Table 2. (Reactions 3-6) Thus, recycling was performed 5 times by using the obtained distillation residue for the next reaction.
- the reaction mass composition after neutralization was such that the yield of ⁇ -mercaptopropionic acid was 79.3 mol%, thiodipropionic acid was 12.0 mol% and dithiodipropionic acid was 8.7 mol% as by-products. .
- the same post-treatment as in Example 1 was performed to obtain 16.2 g (0.152 mol) of ⁇ -mercaptopropionic acid having a purity of 99.9% as a main fraction.
- the yield based on the charged acrylic acid was 76.1%.
- Comparative Example 2 Prepare a five-necked flask equipped with a stirrer, thermometer, cooling tube, dropping funnel, and blowing tube, and after charging 20.6 g (0.50 mol) of 97% sodium hydroxide and 43.3 g of water, uniformly Stir until. While the flask was heated in an oil bath and the internal temperature was maintained at 45 to 50 ° C., 14.4 g (0.20 mol) of acrylic acid was dropped from the dropping funnel over about 0.5 hours.
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Abstract
Description
β-メルカプトカルボン酸の製造方法としては、以下のようなものが挙げられる。
[1]常圧下、硫化水素と、式:XOH(XはNa、Kを示す。)で表される水酸化アルカリと、下記一般式(1):
前記工程で得られた反応液を酸で中和する工程と、を含み、
前記水酸化アルカリの量は、前記不飽和カルボン酸および前記硫化水素の合計モル数以上であることを特徴とする、下記一般式(3)
で表されるβ-メルカプトカルボン酸の製造方法。
本発明のβ-メルカプトカルボン酸の製造方法は以下の工程aおよび工程bを有する。
各工程を順に説明する。
常圧下、硫化水素と、式:XOH(XはNa、Kを示す。)で表される水酸化アルカリと、下記一般式(1)で表される不飽和カルボン酸と、を反応させ、下記一般式(2)で表される化合物を含む反応液を得る。
本発明において、工程aは、下記の方法により行うことができる。
(2)水酸化アルカリ水溶液に、硫化水素を吹き込み、次いで一般式(1)で表される不飽和カルボン酸を添加して反応させる。
なお、方法(3)の場合、水酸化アルカリの量には、予め不飽和カルボン酸アルカリ塩を生成するために用いた水酸化アルカリの量を含む。
工程aで得られた反応液を酸で中和し、一般式(2)で表される化合物から下記一般式(3)で表されるβ-メルカプトカルボン酸を得る。
本発明においては、β-メルカプトカルボン酸の収率を向上させる観点から、生成するジチオジカルボン酸を金属で還元する工程を含むことができる。なお、この還元工程は、工程b(中和工程)の後、または工程bと同時に行うことができる。
かかる工程を繰り返し行うことにより、β-メルカプトカルボン酸の最終的な収率を向上させることができる。
攪拌装置、温度計、冷却管、滴下ロート、吹込み管を備えた5口フラスコを準備し、97%水酸化ナトリウム36.3g(0.88mol)と水43.3gを装入後、均一になるまで攪拌を行なった。フラスコをオイルバスで加熱し内温を45~50℃に保持しながら滴下ロートからアクリル酸14.4g(0.20mol)を0.5時間かけて滴下した。
滴下終了後同温度で液化硫化水素ボンベ(住友精化株式会社製)よりフロー流量計を経由し反応液中に硫化水素ガスを12.6g(0.37mol)を88分間かけて吹き込んだ。吹込み終了後、100℃まで昇温し同温度で8時間反応を行なった。なお、反応開始5時間で反応液をHPLCにて定量分析したところ、β-メルカプトプロピオン酸ナトリウム塩が76.1mol%、副生物としてチオジプロピオン酸ナトリウム塩が23.1mol%、ジチオジプロピオン酸ナトリウム塩が0.3mol%生成していた。
反応終了後、反応液を定量分析した結果、β-メルカプトプロピオン酸ナトリウム塩が86mol%、副生物としてチオジプロピオン酸ナトリウム塩が13mol%、ジチオジプロピオン酸ナトリウム塩が0.4mol%生成していた。
反応系内に窒素をバブリングさせながら、35%硫酸水129.5g(0.462mol)を2.5時間かけて滴下し反応液を中和した。このとき発生した硫化水素は冷却間上部より系外に除外した。また中和後の反応マス組成はβ-メルカプトプロピオン酸は86mol%、副生物であるチオジプロピオン酸が13mol%、ジチオジプロピオン酸が0.3mol%であった。
脱ガス終了後、酢酸ブチル18.0gを装入し抽出操作を行った。分液して得られた水層はさらに酢酸ブチル18.0gを装入し同様の抽出操作を計3回実施した。
3回の抽出で得られた酢酸ブチル層は一つにあわせた後エバポレーターを用いて減圧下酢酸ブチルを留去した。得られた濃縮液は単管付帯の蒸留装置の釜に装入し1.2KPaの減圧下で蒸留を行なった。蒸留は釜温が150℃にまで上がったところで終了した。本釜残の性状は100℃でも流動性があるものであった。主留分として純度99.9%のβ-メルカプトプロピオン酸17.5g(0.165mol)を得た。アクリル酸に対する収率は82.5%であった。
攪拌装置、温度計、冷却管、滴下ロート、吹込み管を備えた5口フラスコを準備し、97%水酸化ナトリウム36.3g(0.88mol)と水43.3gを装入後、均一になるまで攪拌を行なった。フラスコをオイルバスで加熱し内温を45~50℃に保持しながら滴下ロートからアクリル酸14.4g(0.20mol)を0.5時間かけて滴下した。
滴下終了後同温度で液化硫化水素ボンベ(住友精化株式会社製)よりフロー流量計を経由し反応液中に硫化水素ガス12.6g(0.37mol)を88分間かけて吹き込んだ。吹込み終了後、100℃まで昇温し同温度で8時間反応を行なった。
反応終了後、反応液をHPLCにて定量分析したところ、β-メルカプトプロピオン酸ナトリウム塩が86.1mol%、副生物としてチオジプロピオン酸ナトリウム塩が12.9mol%、ジチオジプロピオン酸ナトリウム塩が0.4mol%生成していた。
反応系内にFe粉0.04g(0.0007mol)装入後、窒素をバブリングさせながら、35%硫酸水129.5g(0.462mol)を2.5時間かけて滴下し反応液を還元及び中和した。このとき発生した硫化水素は冷却管上部より系外に除外した。中和後の反応マス組成はβ-メルカプトプロピオン酸は86.5mol%、副生物であるチオジプロピオン酸が12.9mol%であり、ジチオジプロピオン酸は検出されなかった。
攪拌装置、温度計、冷却管、滴下ロート、吹込み管を備えた5口フラスコを準備し、97%水酸化ナトリウム36.3g(0.88mol)と水43.3g、硫黄0.072g(0.0022mol)を装入後、均一になるまで攪拌を行なった。
フラスコをオイルバスで加熱し内温を45~50℃に保持しながら滴下ロートからアクリル酸14.4g(0.20mol)を約0.5時間かけて滴下した。
滴下終了後同温度で液化硫化水素ボンベ(住友精化株式会社製)よりフロー流量計を経由し反応液中に硫化水素ガス12.6g(0.37mol)を88分間かけて吹き込んだ。吹込み終了後、100℃まで昇温し反応を開始した。反応マスのラップ分析を実施しながら反応を行なったところ、反応開始2時間でβ-メルカプトプロピオン酸ナトリウム塩の収率が84.0mol%、副生物としてチオジプロピオン酸ナトリウム塩が14.9mol%、ジチオジプロピオン酸ナトリウム塩が0.5mol%生成していた。
反応開始5時間で終了したところ、β-メルカプトプロピオン酸ナトリウム塩の収率は87.4mol%、副生物としてチオジプロピオン酸ナトリウム塩が11.8mol%、ジチオジプロピオン酸ナトリウム塩が0.8mol%生成していた。
攪拌装置、温度計、冷却管、滴下ロート、吹込み管を備えた5口フラスコを準備し、97%水酸化ナトリウム47.0g(1.14mol)と水54.5g、硫黄0.072g(0.0022mol)を装入後、均一になるまで攪拌を行なった。
フラスコをオイルバスで加熱し内温を45~50℃に保持しながら滴下ロートからアクリル酸14.4g(0.20mol)を0.5時間かけて滴下した。
滴下終了後同温度で液化硫化水素ボンベ(住友精化株式会社製)よりフロー流量計を経由し反応液中に硫化水素ガス17.7g(0.52mol)を90分間かけて吹き込んだ。吹込み終了後、100℃まで昇温し同温度で8時間反応を行なった。
反応終了後、反応液をHPLCにて定量分析したところ、β-メルカプトプロピオン酸ナトリウム塩が94.8mol%、副生物としてチオジプロピオン酸ナトリウム塩が4.6mol%、ジチオジプロピオン酸ナトリウム塩が0.2mol%生成していた。
実施例1と同様の操作を行い、主留分として純度99.9%のβ-メルカプトプロピオン酸17.5g(0.165mol)、蒸留釜の残渣(蒸留残渣(A))として2.8g(β-メルカプトプロピオン酸15.7wt%(0.004mol)、チオジプロピオン酸81.5wt%(0.012mol)、ジチオジプロピオン酸2.3wt%(0.0003mol)を得た(反応1)。
攪拌装置、温度計、冷却管、滴下ロート、吹込み管を備えた5口フラスコを準備し、97%水酸化ナトリウム36.3g(0.88mol)と水43.3gを装入後、均一になるまで攪拌を行なった。この水酸化ナトリウム水溶液中に90~95℃に保温し流動性がある状態の蒸留残渣(A)2.8g(組成比:β-メルカプトプロピオン酸15.7wt%、チオジプロピオン酸81.5wt%、ジチオジプロピオン酸2.3wt%)をゆっくりと添加した。内温を45~50℃に保持しながら滴下ロートからアクリル酸12.24g(0.17mol)を0.5時間かけて滴下した。
滴下終了後同温度で液化硫化水素ボンベ(住友精化株式会社製)よりフロー流量計を経由し反応液中に硫化水素ガス12.6g(0.37mol)を90分間かけて吹き込んだ。吹込み終了後、100℃まで昇温し同温度で8時間反応を行なった。
反応終了後、反応液をHPLCにて定量分析したところ、β-メルカプトプロピオン酸ナトリウム塩が0.172mol、副生物としてチオジプロピオン酸ナトリウム塩が0.013mol、ジチオジプロピオン酸ナトリウム塩が0.0006mol生成していた。
実施例1と同様に中和、抽出、蒸留操作を行い、主留分として純度99.9%のβ-メルカプトプロピオン酸17.5g(0.165mol)を得た(反応2)。初回と蒸留残渣リサイクル1回目の反応で使用したアクリル酸(14.4g+12.2g)に対するβ-メルカプトプロピオン酸の収率は89.2%であった。
また蒸留釜の残渣(蒸留残渣(B))として2.9g(β-メルカプトプロピオン酸15.3wt%(0.004mol)、チオジプロピオン酸79.3wt%(0.013mol)、ジチオジプロピオン酸4.4wt%(0.0006mol))を得た。
実施例5における反応に供した原料、得られた反応生成物の組成等を表1に示す。
実施例1と同様に反応を行なった(反応1)。そして、反応1で得られた蒸留後の蒸留残渣(A)を用い、反応に供する原料等の量を表2に記載されたように変更した以外は、実施例4と同様の条件で反応を行なった(反応2)。同様に、前反応で得られた蒸留残渣を用いて、反応に供する原料等の量を表2に記載されたように変更した以外は、実施例4と同様の条件で4回反応を行なった(反応3~6)
このように、得られた蒸留残渣を次の反応に用いることにより、5回リサイクルを行った。その結果、初回(反応1)及びリサイクル1回~5回(反応2~6)実施するのに使用したアクリル酸に対して、蒸留主留として得られたβ-メルカプトプロピオン酸(純度99.9%)の収率は94.4%となった。
実施例6における反応に供した原料、得られた反応生成物の組成等を表2に示す。
攪拌装置、温度計、冷却管、滴下ロート、吹込み管を備えた5口フラスコを準備し、97%水酸化ナトリウム21.0g(0.51mol)と水41.6gを装入後、70%水硫化ソーダ(和光純薬製)を29.6g(0.37mol)装入し均一になるまで攪拌を行なった。
フラスコをオイルバスで加熱し内温を45~50℃に保持しながら滴下ロートからアクリル酸14.4g(0.20mol)を約0.5時間かけて滴下した。滴下終了後、100℃まで昇温し同温度で8時間反応を行なった。
反応終了後、反応マスをHPLCにて分析したところ、β-メルカプトプロピオン酸ナトリウム塩の収率は87.3mol%、副生物としてチオジプロピオン酸ナトリウム塩が12.0mol%、ジチオジプロピオン酸ナトリウム塩が0.7mol%生成していた。
反応系内に窒素をバブリングさせながら、35%硫酸水129.5g(0.462mol)を2.5時間かけて滴下し反応液を中和した。このとき発生した硫化水素はコンデンサー上部より系外に除外した。また中和後の反応マス組成はβ-メルカプトプロピオン酸の収率は79.3mol%、副生物としてチオジプロピオン酸が12.0mol%、ジチオジプロピオン酸が8.7mol%と増加していた。
脱ガス終了後、実施例1と同様の後処理を行ない、主留分として純度99.9%のβ-メルカプトプロピオン酸16.2g(0.152mol)を得た。仕込みのアクリル酸に対する収率は76.1%であった。
攪拌装置、温度計、冷却管、滴下ロート、吹込み管を備えた5口フラスコを準備し、97%水酸化ナトリウム20.6g(0.50mol)と水43.3gを装入後、均一になるまで攪拌を行なった。
フラスコをオイルバスで加熱し内温を45~50℃に保持しながら滴下ロートからアクリル酸14.4g(0.20mol)を約0.5時間かけて滴下した。
滴下終了後同温度で液化硫化水素ボンベ(住友精化株式会社製)よりフロー流量計を経由し反応液中に硫化水素ガス12.6g(0.37mol)を88分間かけて吹き込んだ。吹込み終了後、100℃まで昇温し同温度で8時間反応を行なった。
反応終了後、反応マスをHPLCにて定量分析したところ、β-メルカプトプロピオン酸ナトリウム塩が49.3mol%、副生物としてチオジプロピオン酸ナトリウム塩が48.8mol%、ジチオジプロピオン酸ナトリウム塩が1.3mol%生成していた。
実施例1~4、比較例1~2の結果を表3にまとめて示す。
β-MPA : β-メルカプトプロピオン酸ナトリウム塩
S体 : チオジプロピオン酸ナトリウム塩
SS体 : ジチオジプロピオン酸ナトリウム塩
Claims (3)
- 常圧下、硫化水素と、式:XOH(XはNa、Kを示す。)で表される水酸化アルカリと、下記一般式(1):
前記工程で得られた反応液を酸で中和する工程と、を含み、
前記水酸化アルカリの量は、前記不飽和カルボン酸および前記硫化水素の合計モル数以上であることを特徴とする、下記一般式(3)
で表されるβ-メルカプトカルボン酸の製造方法。 - 反応液を得る前記工程は、硫黄存在下で行われることを特徴とする、請求項1に記載のβ-メルカプトカルボン酸の製造方法。
- 反応液を酸で中和する前記工程は、β-メルカプトカルボン酸から生成したジチオジカルボン酸を金属で還元する工程を含むことを特徴とする、請求項1または2に記載のβ-メルカプトカルボン酸の製造方法。
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