JPH049363A - Production of beta-mercaptopropionic acid - Google Patents
Production of beta-mercaptopropionic acidInfo
- Publication number
- JPH049363A JPH049363A JP31479690A JP31479690A JPH049363A JP H049363 A JPH049363 A JP H049363A JP 31479690 A JP31479690 A JP 31479690A JP 31479690 A JP31479690 A JP 31479690A JP H049363 A JPH049363 A JP H049363A
- Authority
- JP
- Japan
- Prior art keywords
- acid
- alkali metal
- alkali
- sulfide
- thiodiprobionic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 title description 3
- 239000002253 acid Substances 0.000 claims abstract description 53
- 239000000243 solution Substances 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims abstract description 15
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000003513 alkali Substances 0.000 claims description 23
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 11
- 229910001854 alkali hydroxide Inorganic materials 0.000 claims description 11
- 239000011259 mixed solution Substances 0.000 claims description 3
- 150000001447 alkali salts Chemical class 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 229910052979 sodium sulfide Inorganic materials 0.000 abstract description 13
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 abstract description 13
- 238000010438 heat treatment Methods 0.000 abstract description 8
- 239000006227 byproduct Substances 0.000 abstract description 7
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 abstract description 5
- 239000007864 aqueous solution Substances 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 4
- 229920005989 resin Polymers 0.000 abstract description 4
- 239000011347 resin Substances 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- -1 alkali metal salt Chemical class 0.000 abstract description 3
- 239000003431 cross linking reagent Substances 0.000 abstract description 3
- 239000003822 epoxy resin Substances 0.000 abstract description 3
- 229920000647 polyepoxide Polymers 0.000 abstract description 3
- 230000003247 decreasing effect Effects 0.000 abstract description 2
- ODJQKYXPKWQWNK-UHFFFAOYSA-N 3,3'-Thiobispropanoic acid Chemical compound OC(=O)CCSCCC(O)=O ODJQKYXPKWQWNK-UHFFFAOYSA-N 0.000 abstract 2
- 239000003490 Thiodipropionic acid Substances 0.000 abstract 2
- 229910052783 alkali metal Inorganic materials 0.000 abstract 2
- 229910052977 alkali metal sulfide Inorganic materials 0.000 abstract 2
- 150000001875 compounds Chemical class 0.000 abstract 2
- 235000019303 thiodipropionic acid Nutrition 0.000 abstract 2
- 229910052936 alkali metal sulfate Inorganic materials 0.000 abstract 1
- 229920000058 polyacrylate Polymers 0.000 abstract 1
- 239000004848 polyfunctional curative Substances 0.000 abstract 1
- 150000003839 salts Chemical class 0.000 abstract 1
- 238000000034 method Methods 0.000 description 27
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 239000010446 mirabilite Substances 0.000 description 5
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 description 4
- 239000003381 stabilizer Substances 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 2
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- DCXXMTOCNZCJGO-UHFFFAOYSA-N Glycerol trioctadecanoate Natural products CCCCCCCCCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCC DCXXMTOCNZCJGO-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 2
- 125000005396 acrylic acid ester group Chemical group 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- RSIJVJUOQBWMIM-UHFFFAOYSA-L sodium sulfate decahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].[O-]S([O-])(=O)=O RSIJVJUOQBWMIM-UHFFFAOYSA-L 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-M hydrosulfide Chemical compound [SH-] RWSOTUBLDIXVET-UHFFFAOYSA-M 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000006193 liquid solution Substances 0.000 description 1
- IHYNKGRWCDKNEG-UHFFFAOYSA-N n-(4-bromophenyl)-2,6-dihydroxybenzamide Chemical compound OC1=CC=CC(O)=C1C(=O)NC1=CC=C(Br)C=C1 IHYNKGRWCDKNEG-UHFFFAOYSA-N 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- DPLVEEXVKBWGHE-UHFFFAOYSA-N potassium sulfide Chemical compound [S-2].[K+].[K+] DPLVEEXVKBWGHE-UHFFFAOYSA-N 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- HYHCSLBZRBJJCH-UHFFFAOYSA-M sodium hydrosulfide Chemical compound [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、例えば硫化ナトリウムとアクリルニトリルか
らβ−メルカプトプロビオン酸を製造する際に副生ずる
チオジプロビオン酸を再利用するβ−メルカプトプロビ
オン酸の製造法に関し、特に過剰の水酸化アルカリの存
在下に、硫化アルカリと反応させてβ−メルカプトプロ
ビオン酸をいっそう高収率で製造する方法に関する。Detailed Description of the Invention (Field of Industrial Application) The present invention is directed to the production of β-mercaptoprobionic acid, which reuses thiodiprobionic acid, which is a by-product during the production of β-mercaptoprobionic acid from, for example, sodium sulfide and acrylonitrile. In particular, it relates to a method for producing β-mercaptoprobionic acid at a higher yield by reacting it with an alkali sulfide in the presence of an excess of alkali hydroxide.
（従来の技術）
β−メルカプトプロビオン酸は、レンズ用樹脂の原料、
アクリル酸エステルポリマーの架橋剤、エポキシ樹脂の
硬化剤、塩化ビニルの安定剤などの用途があり、近年、
その生産量が急増している。(Prior art) β-mercaptoprobionic acid is a raw material for lens resin,
In recent years, it has been used as a crosslinking agent for acrylic acid ester polymers, a curing agent for epoxy resins, and a stabilizer for vinyl chloride.
Its production is rapidly increasing.
β−メルカプトプロビオン酸の製造法としては、従来、
クロール法、チオ尿素法、水硫化ソーダ法（特開昭５８
−１９８４６０号参照）などが存在する。これに対し、
本発明者は、既に特公昭６３−６５４５号において硫化
ナトリウムとアクリルニトリルを反応させる方法を提案
している。この方法は、従来の方法に比べて、工程が簡
単で全反応に要する時間が短いので経済的てあり、排水
処理も簡単であって公害問題が発生する恐れが生じない
という利点がある。Conventionally, methods for producing β-mercaptoprobionic acid include
Kroll method, thiourea method, sodium hydrogen sulfide method (Japanese Patent Application Laid-open No. 58
-198460). On the other hand,
The present inventor has already proposed a method of reacting sodium sulfide and acrylonitrile in Japanese Patent Publication No. 63-6545. Compared to conventional methods, this method has the advantage that it is economical because the steps are simple and the time required for the entire reaction is short, and wastewater treatment is simple and does not pose a risk of pollution problems.
（発明が解決しようとする課題）
本発明者が提案した特公昭６３−６５４５号の方法では
、副生物としてアンモニアガス、芒硝液及びチオジプロ
ビオン酸が発生するけれども、アンモニアガスは水に吸
収させると純粋なアンモニア水となり、芒硝液は冷却し
て結晶芒硝とするとそのまま他の用途に使用することが
できる。また、副生ずるチオジプロビオン酸は、従来、
２−エチルヘキシルアルコールやステアリンアルコール
などでエステル化すると、ポリプロピレンの安定剤又は
各種の樹脂用の酸化防止剤としての用途があった。しか
しながら、これらの用途には、近年、より安価な他の化
学薬品が使用され始め、チオジプロビオン酸の需要が減
少する傾向があり、将来においてはチオジプロビオン酸
の処理に困る恐れがある。(Problems to be Solved by the Invention) In the method of Japanese Patent Publication No. 63-6545 proposed by the present inventor, ammonia gas, mirabilite solution and thiodiprobionic acid are generated as by-products, but ammonia gas becomes pure when absorbed in water. When the mirabilite solution is cooled and turned into crystalline mirabilite, it can be used as is for other purposes. In addition, thiodiprobionic acid, which is a by-product, has traditionally been
When esterified with 2-ethylhexyl alcohol or stearin alcohol, it has been used as a stabilizer for polypropylene or as an antioxidant for various resins. However, in recent years, other cheaper chemicals have begun to be used for these applications, and the demand for thiodiprobionic acid tends to decrease, and there is a possibility that it will be difficult to treat thiodiprobionic acid in the future.
本発明は、チオジプロビオン酸の処理に関する前記の問
題点を解決するために提案されたものであり、需要が減
りつつあるチオジプロビオン酸から、依然として需要が
盛んなβ−メルカプトプロビオン酸を容易に製造する方
法を提供することを目的としている。また、本発明の他
の目的は、安価な水酸化アルカリの使用量を増やす一方
、高価な硫化アルカリの使用量を減らし、しかもβ−メ
ルカプトプロビオン酸をいっそう高い収率で製造する方
法を提供することである。The present invention was proposed to solve the above-mentioned problems regarding the treatment of thiodiprobionic acid, and it is possible to easily produce β-mercaptoprobionic acid, which is still in high demand, from thiodiprobionic acid, whose demand is decreasing. The purpose is to provide a method. Another object of the present invention is to provide a method for producing β-mercaptoprobionic acid at an even higher yield by increasing the amount of inexpensive alkali hydroxide used while reducing the amount of expensive alkali sulfide used. It is to be.
（課題を解決するための手段）
上記目的を達成するために、本発明に係るβ−メルカプ
トプロビオン酸の製造法では、出発物質はチオジプロビ
オン酸（５（ＣＨ２ＣＨ２ＣＯＯＨ） ２ ）である。(Means for Solving the Problems) In order to achieve the above object, in the method for producing β-mercaptoprobionic acid according to the present invention, the starting material is thiodiprobionic acid (5(CH2CH2COOH) 2 ).
このチオジプロビオン酸は、一般に硫化ナトリウムとア
クリルニトリルを反応させる方法（特公昭６３−６５４
５号）において副生じたものを再利用すると好ましいけ
れども、他の公知方法における副生物であっても、又は
本発明方法に使用するために製造してもよい。チオジプ
ロビオン酸をアルカリ塩にするために用いる水酸化アル
カリは、通常、水酸化ナトリウム、水酸化カリウムなど
である。チオジプロビオン酸アルカリと反応させる硫化
アルカリとしては、硫化ナトリウム、硫化カリウムなど
が例示でき、これを水に加熱溶解させて高濃度の水溶液
にして使用しても、水硫化アルカリ、適量の水酸化アル
カリ及び水を加熱混合して製造してもよい。チオジプロ
ビオン酸アルカリは、高濃度の硫化アルカリ水溶液中に
直接添加すればよく、この反応は、一般に１１０〜１３
０ ”Ｃで約１時間から数時間加熱することによって完
了する。This thiodiprobionic acid is generally produced by a method of reacting sodium sulfide with acrylonitrile (Japanese Patent Publication No. 63-654).
Although it is preferable to recycle the by-products in No. 5), they may also be by-products from other known methods or may be produced for use in the method of the present invention. The alkali hydroxide used to convert thiodiprobionic acid into an alkali salt is usually sodium hydroxide, potassium hydroxide, or the like. Examples of alkali sulfides to be reacted with alkali thiodiprobionic acid include sodium sulfide and potassium sulfide. Even if this is heated and dissolved in water and used as a highly concentrated aqueous solution, the alkali hydrosulfide, an appropriate amount of alkali hydroxide and It may also be produced by heating and mixing water. Alkali thiodiprobionic acid may be added directly to a highly concentrated aqueous alkali sulfide solution, and this reaction generally takes place at a concentration of 110 to 13
Complete by heating at 0''C for about 1 hour to several hours.
また、チオジプロビオン酸アルカリは、過剰の水酸化ア
ルカリの存在下に、より少量の硫化アルカリと効果的に
反応し、前記と同様にβ−メルカプトプロビオン酸アル
カリに移行する。In addition, alkali thiodiprobionic acid reacts effectively with a smaller amount of alkali sulfide in the presence of excess alkali hydroxide, and converts to alkali β-mercaptoprobionic acid in the same manner as described above.
５（ＣＨ２ＣＨ２ＣＯＯＮａ）２＋ Ｎａ２Ｓ ＋ ２
ＮａＳＣＨ２ＣＨ２ＣＯＯＮａ得た反応溶液を硫酸、塩
酸などの塩基酸で酸性化すると、下記のようにβ−メル
カプトプロビオン酸を製造することができる。5(CH2CH2COONa)2+ Na2S + 2
When the reaction solution obtained is acidified with a basic acid such as sulfuric acid or hydrochloric acid, β-mercaptoprobionic acid can be produced as described below.
Ｎａ５ＣＨ２ＣＨ２ＣＯＯＮａ ＋ Ｈ２ＳＯ−４Ｈ
５ＣＨ２ＣＨ２ＣＯＯＨ＋ Ｎａ２５Ｏａ （回収）使
用する反応容器がガラス容器であると、生成したβ−メ
ルカプトプロビオン酸が酸化によって失われることが少
なく、鉄製反応釜なとては酸化防止のために不活性ガス
を充填すると好ましい。Na5CH2CH2COONa + H2SO-4H
5CH2CH2COOH+ Na25Oa (Recovery) When the reaction vessel used is a glass vessel, the generated β-mercaptoprobionic acid is less likely to be lost due to oxidation, and iron reaction vessels are filled with inert gas to prevent oxidation. Then it is preferable.
（作用）
本発明方法において、チオジプロビオン酸アルカリを硫
化アルカリ水溶液中に添加して反応させるには、高濃度
の硫化アルカリ水溶液を使用し、且つ１１０〜１３０°
Ｃで約１時間から数時間加熱することが必要である。ま
た、本発明の他の方法では、チオジプロビオン酸アルカ
リを比較的少量の硫化アルカリと反応させる際に、過剰
の水酸化アルカリが触媒的な作用をしてβ−メルカプト
プロビオン酸アルカリの収率が高くなるものと推定でき
る。(Function) In the method of the present invention, in order to add alkali thiodiprobionic acid to an aqueous alkali sulfide solution and cause the reaction to occur, a highly concentrated aqueous alkali sulfide solution is used, and
It is necessary to heat for about 1 hour to several hours at C. In addition, in another method of the present invention, when alkali thiodiprobionic acid is reacted with a relatively small amount of alkali sulfide, the excess alkali hydroxide acts as a catalyst and the yield of alkali β-mercaptoprobionic acid is reduced. It is estimated that the price will increase.
本発明方法は、単にβ−メルカプトプロビオン酸を製造
する面から考慮すれば、硫化ナトリウムとアクリルニト
リルを反応させる方法（特公昭６３−６５４５号）に比
べて、コストや収率などの点で特に優れているわけでは
ないが、前記の方法と併用した場合に多量のβ−メルカ
ブトブロピオン酸を効率よく製造でき、且つ副生物が少
なくなってきわめて有効である。From the perspective of simply producing β-mercaptoprobionic acid, the method of the present invention is superior in terms of cost and yield compared to the method of reacting sodium sulfide and acrylonitrile (Japanese Patent Publication No. 63-6545). Although not particularly superior, when used in combination with the above-mentioned method, a large amount of β-mercabutopropionic acid can be efficiently produced and the amount of by-products is reduced, making it extremely effective.
（実施例） 次に本発明方法を実施例に基づいて説明する。(Example) Next, the method of the present invention will be explained based on examples.
実施例１
チオジプロビオンｆｉ３０ｇ及び３３％水酸化ナトリウ
ム４０ｇとを混合して、チオジプロビオン酸ナトリウム
を製造する。このナトリウム塩を、７０％水硫化ナトリ
ウム４０ｇ、３３％水酸化ナトリウム６０ｇ及び水２０
ｇを加熱して造った硫化ナトリウム水溶液中に加え、更
に加熱して液温を１２３°Ｃに上げる。Example 1 Sodium thiodiprobionate is prepared by mixing 30 g of thiodiprobione fi and 40 g of 33% sodium hydroxide. This sodium salt was mixed with 40 g of 70% sodium bisulfide, 60 g of 33% sodium hydroxide and 20 g of water.
Add g to a sodium sulfide aqueous solution prepared by heating, and further heat to raise the liquid temperature to 123°C.
この混合溶液を１２０〜１３０°Ｃで１時間反応させて
から、６２％硫酸８０ｇと水３５０ｃｍ３との溶液中に
添加する。２〜３分間煮沸して反応の際に発生した硫化
水素を飛散させた後に、反応溶液を冷却し、水を加えて
容量を正確に１０００ｃ ｍ ３とする。This mixed solution is reacted at 120-130°C for 1 hour and then added to a solution of 80 g of 62% sulfuric acid and 350 cm 3 of water. After boiling for 2-3 minutes to scatter the hydrogen sulfide generated during the reaction, the reaction solution is cooled and water is added to make the volume exactly 1000 cm 3 .
この反応溶液１０ｃｍ３をホールピペットに取り、１／
１ ＯＮヨウ素で滴定すると、指示薬（でんぶん液）で
２４．７ｃｍ３消費する結果、得たβ−メルカプトプロ
ビオン酸は２６．７ｇであることが判明する。これは、
チオジプロビオン酸に対して約８９％の収率であり、理
論収率では約７５％である。Transfer 10 cm3 of this reaction solution to a whole pipette and
Titration with 1 ON iodine reveals that 24.7 cm3 of the indicator (starch solution) was consumed, resulting in 26.7 g of β-mercaptoprobionic acid obtained. this is,
The yield is about 89% based on thiodiprobionic acid, and the theoretical yield is about 75%.
実施例２
チオジプロビオン酸７２ｇに３３％水酸化ナトリウム９
８ｇを添加して、チオジプロビオン酸ナトリウムを製造
する。このナトリウム塩を、６０％フレーク硫化ナトリ
ウム１２５ｇを水６０ ｃｍ３て加熱溶解させ方硫化ナ
トリウム水溶液中に撹拌しながら加え、更に加熱して液
温を上げる。Example 2 33% sodium hydroxide 9 to 72 g of thiodiprobionic acid
Add 8 g to produce sodium thiodiprobionate. This sodium salt is added to an aqueous sodium sulfide solution by heating and dissolving 125 g of 60% flake sodium sulfide in 60 cm3 of water, and then heating the solution to raise the temperature of the solution.
この混合溶液を１２３〜１２７°Ｃで２．５時間反応さ
せてから、６２．５％硫酸２６０ｇと水２００ｃｍ３と
の溶液中に撹拌しながら流入させる。This mixed solution is reacted at 123-127° C. for 2.5 hours, and then poured into a solution of 260 g of 62.5% sulfuric acid and 200 cm 3 of water with stirring.
反応溶液を冷却して４０″Ｃで析出した芒硝をン戸取し
、５戸液を１００ｃｍ３のジプロピルエーテル４回抽出
する。一方、析出した芒硝を１００ｃｍ３のジプロピル
エーテルで２０洗浄し、この洗浄溌を抽出ジプロピルエ
ーテルと合算する。合算したジプロピルエーテルを常圧
で蒸留して回収した後に、１０ｍｍＨｇの減圧下で蒸留
してβーメルカプトプロピオン＠５５ｇを得る（純度９
８，１％）。The reaction solution was cooled and the precipitated Glauber's salt was collected at 40"C, and the 5-liquid solution was extracted four times with 100 cm3 of dipropyl ether. Meanwhile, the precipitated Glauber's salt was washed with 100 cm3 of dipropyl ether for 20 minutes. The washings are combined with extracted dipropyl ether. The combined dipropyl ether is recovered by distillation at normal pressure, and then distilled under reduced pressure of 10 mmHg to obtain 55 g of β-mercaptopropion (purity 9).
8.1%).
また、フラスコ残漬から未反応の粗チオジプロビオン酸
１５ｇを回収できる。Furthermore, 15 g of unreacted crude thiodiprobionic acid can be recovered from the residue in the flask.
実施例３
水３００ｃｍ３にチオジプロビオン酸２２０ｇ（約１．
２モル）及び４７％水酸化ナトリウム４３０ｇ （約５
．１モル）を加えて溶解し、チオジプロビオン酸ナトリ
ウムにした後に、６０％硫化ナトリウム２８０ｇ （約
２．２モル）を添加して１３０°Ｃで１時間反応させる
。次に水５００ｃｍ３と６２．５％硫酸４６０ｃｍ３と
添加して酸性として油状物を分離し、残液をイソプロピ
ルエーテル２００ｇで４回抽出する。全抽出液を混合し
、イソプロピルエーテルを減圧蒸留で回収する。油状物
の粗βーメルカプトプロピオン酸を減圧蒸留後の留分と
合算すると、β−メルカプトプロビオン酸（１ｏｏ換算
）として２３５ｇを得、これは理論収率で９０％である
。Example 3 220 g of thiodiprobionic acid (approximately 1.
2 moles) and 430 g of 47% sodium hydroxide (approximately 5
．． 1 mol) was added and dissolved to form sodium thiodiprobionate, then 280 g (approximately 2.2 mol) of 60% sodium sulfide was added and reacted at 130°C for 1 hour. The mixture is then acidified by adding 500 cm@3 of water and 460 cm@3 of 62.5% sulfuric acid to separate the oil, and the remaining liquid is extracted four times with 200 g of isopropyl ether. All extracts are mixed and the isopropyl ether is recovered by vacuum distillation. When the oily crude β-mercaptopropionic acid was combined with the fraction after distillation under reduced pressure, 235 g of β-mercaptopropionic acid (calculated as 1 OO) was obtained, which is a theoretical yield of 90%.
（発明の効果）
本発明方法では、チオジプロビオン酸アルカリをＸＫ
？Ｍ度の硫化アルカリ水溶液中に添加して１１０〜１３
０°Ｃで約１時間から数時間加熱反応させるだけで、β
−メルカプトプロビオン酸を容易に製造することができ
る。本発明方法は、硫化ナトリウムとアクリルニド１ノ
ルを反応させる方法（特公昭６３−６５４５号）と併用
した場合に、β−メルカプトプロビオン酸をいっそう低
コスト且っ高収率に製造でき、しかも副生物を少なくす
ることが可能になる。(Effect of the invention) In the method of the present invention, alkali thiodiprobionic acid is
? Added to M degree alkali sulfide aqueous solution to 110-13
By simply heating the reaction at 0°C for about 1 to several hours, β
-Mercaptoprobionic acid can be easily produced. When the method of the present invention is used in combination with the method of reacting sodium sulfide and acrylide 1-nor (Japanese Patent Publication No. 63-6545), it is possible to produce β-mercaptoprobionic acid at a lower cost and in a higher yield. It becomes possible to reduce the number of living things.
本発明の他の方法では、過剰の水酸化アルカリを用いる
ことにより、前記の方法に比べて安価な水酸化アルカリ
の使用量を増やす一方、高価な硫化アルカリの使用量を
減らして経済的に有利である。しかもこの方法は、前記
の方法に比べてもβ−メルカプトプロビオン酸をいっそ
う高い収率で製造できる。In another method of the present invention, by using an excess of alkali hydroxide, the amount of cheap alkali hydroxide used is increased and the amount of expensive alkali sulfide used is reduced, which is economically advantageous. It is. Moreover, this method can produce β-mercaptoprobionic acid in a higher yield than the above-mentioned method.
本発明方法で・製造したβ−メルヵブトブ口ビオン酸は
、レンズ用樹脂の原料、アクリル酸エステルポリマーの
架橋剤、エポキシ樹脂の硬化剤、塩化ビニルの安定剤な
どとして盛んな需要があり、依然としてその生産量は増
大している。一方、特公詔ａ ３−６５４５号の方法で
発生するチオジプロビオン酸は、２−エチルヘキシルア
ルコールやステアリンアルコールなどでエステル化する
と、安定剤や酸化防止剤としての用途があったけれども
、近年、これらの用途には他の化学薬品が使用され始め
ている。このため、チオジプロビオン酸の需要が減る傾
向があり、将来、処理に困る恐れがあるチオジプロビオ
ン酸を、本発明方法において原料として使用することは
有益である。The β-mercabutobionic acid produced by the method of the present invention is in great demand as a raw material for lens resins, a crosslinking agent for acrylic acid ester polymers, a curing agent for epoxy resins, a stabilizer for vinyl chloride, etc., and is still in high demand. Production is increasing. On the other hand, thiodiprobionic acid generated by the method of Special Public Rescript No. A 3-6545 has been used as a stabilizer and antioxidant when esterified with 2-ethylhexyl alcohol or stearin alcohol. Other chemicals are beginning to be used in the application. For this reason, the demand for thiodiprobionic acid tends to decrease, and it is advantageous to use thiodiprobionic acid, which may be difficult to process in the future, as a raw material in the method of the present invention.
Claims (1)
カリ塩とした後に、硫化アルカリ水溶液と混合し、この
混合溶液を所定時間加熱して反応させてから、反応溶液
を硫酸、塩酸などの塩基酸で酸性化しているβ−メルカ
プトプロビオン酸の製造法。 ２、チオジプロビオン酸に過剰の水酸化アルカリを加え
て生成するチオジプロビオン酸アルカリを、過剰の水酸
化アルカリの存在下に、比較的少量の硫化アルカリと反
応させてβ−メルカプトプロビオン酸アルカリとしてか
ら、反応溶液を硫酸、塩酸などの塩基酸で酸性化してい
るβ−メルカプトプロビオン酸の製造法。[Claims] 1. Add alkali hydroxide to thiodiprobionic acid to make an alkali salt, mix it with an aqueous alkali sulfide solution, heat this mixed solution for a predetermined period of time to react, and then add the reaction solution to sulfuric acid, hydrochloric acid, etc. A method for producing β-mercaptoprobionic acid acidified with a basic acid such as. 2. The alkali thiodiprobionic acid produced by adding an excess alkali hydroxide to thiodiprobionic acid is reacted with a relatively small amount of alkali sulfide in the presence of an excess alkali hydroxide to form an alkali β-mercaptoprobionic acid, A method for producing β-mercaptoprobionic acid in which a reaction solution is acidified with a basic acid such as sulfuric acid or hydrochloric acid.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31479690A JP2709650B2 (en) | 1990-04-24 | 1990-11-19 | Production method of β-mercaptopropionic acid |
| US07/790,369 US5256818A (en) | 1990-11-19 | 1991-11-12 | Method for making β-mercaptopropionic acid |
| FR9114071A FR2669330B1 (en) | 1990-11-19 | 1991-11-15 | PROCESS FOR THE PREPARATION OF BETHA-MERCAPTOPROPIONIC ACID. |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10984290 | 1990-04-24 | ||
| JP2-109842 | 1990-04-24 | ||
| JP31479690A JP2709650B2 (en) | 1990-04-24 | 1990-11-19 | Production method of β-mercaptopropionic acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH049363A true JPH049363A (en) | 1992-01-14 |
| JP2709650B2 JP2709650B2 (en) | 1998-02-04 |
Family
ID=26449559
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP31479690A Expired - Lifetime JP2709650B2 (en) | 1990-04-24 | 1990-11-19 | Production method of β-mercaptopropionic acid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2709650B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5275002A (en) * | 1992-01-22 | 1994-01-04 | Aisin Newhard Co., Ltd. | Pulse tube refrigerating system |
| WO2013076969A1 (en) | 2011-11-21 | 2013-05-30 | 三井化学株式会社 | METHOD FOR PRODUCING β-MERCAPTOCARBOXYLIC ACID |
| US9206119B2 (en) | 2011-11-21 | 2015-12-08 | Mitsui Chemicals Inc. | Process for preparing β-mercaptocarboxylic acid |
-
1990
- 1990-11-19 JP JP31479690A patent/JP2709650B2/en not_active Expired - Lifetime
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5275002A (en) * | 1992-01-22 | 1994-01-04 | Aisin Newhard Co., Ltd. | Pulse tube refrigerating system |
| WO2013076969A1 (en) | 2011-11-21 | 2013-05-30 | 三井化学株式会社 | METHOD FOR PRODUCING β-MERCAPTOCARBOXYLIC ACID |
| JPWO2013076969A1 (en) * | 2011-11-21 | 2015-04-27 | 三井化学株式会社 | Process for producing β-mercaptocarboxylic acid |
| US9133112B2 (en) | 2011-11-21 | 2015-09-15 | Mitsui Chemicals, Inc. | Process for preparing β-mercaptocarboxylic acid |
| US9206119B2 (en) | 2011-11-21 | 2015-12-08 | Mitsui Chemicals Inc. | Process for preparing β-mercaptocarboxylic acid |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2709650B2 (en) | 1998-02-04 |
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