JP3586503B2 - Method for producing tertiary butyl acrylamide - Google Patents
Method for producing tertiary butyl acrylamide Download PDFInfo
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- JP3586503B2 JP3586503B2 JP30329595A JP30329595A JP3586503B2 JP 3586503 B2 JP3586503 B2 JP 3586503B2 JP 30329595 A JP30329595 A JP 30329595A JP 30329595 A JP30329595 A JP 30329595A JP 3586503 B2 JP3586503 B2 JP 3586503B2
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- tertiary butyl
- butyl acrylamide
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Description
【０００１】
【発明の属する技術分野】
本発明は、ターシャリーブチルアクリルアミドの製造方法に関する。
ターシャリーブチルアクリルアミドはアクリロニトリル系合成繊維の改質剤やゴム薬品、塗料等の原材料として有用な物質である。
【０００２】
【従来技術と問題点】
従来、ターシャリーブチルアクリルアミドを製造する方法としては、濃硫酸の存在下、ターシャリーブタノールとアクリロニトリルとを反応せしめ、得られた反応液を水中に添加してターシャリーブチルアクリルアミドを結晶化し分離取得する方法（ジャーナル・オブ・ジ・アメリカン・ソサエテイー、第７３巻、第９号、４０７６頁（１９５１年））や反応混合物をアルカリ水溶液で部分中和してＰＨ２〜４とし、キシレンなどのアミド用炭化水素溶剤に抽出、分離する方法（特公昭４３−８０８７号公報）などがある。しかし、これらの方法では反応途中で重合が生じるとか、反応液が着色するという問題がある。さらに、前者の方法は、晶析取得の際に副生アクリル酸等の酸性物質が目的物ターシャリーブチルアクリルアミド中に混入して純度を低下させるばかりか、得られたターシャリーブチルアクリルアミドを用いて重合した際にポリマーは臭気を生じるという問題もある。また、分離取得に当たっては、強酸性条件下で結晶析出および分離を行うため高価な耐酸性の結晶析出槽や分離器が必要となる。一方、後者の方法は、原材料中に存在する微量の金属イオンによる悪影響を少なくすることを目的に、反応混合物をアルカリ水溶液で適度に中和をしながら抽出、分離を行うため、煩雑な工程を必要とするなど操作上問題があった。
【０００３】
【発明が解決しようとしている課題】
本発明の目的は、これら従来技術における問題点を改善すべくなされたもので、反応時における重合防止と共に不純物が少なく着色のない高品質のターシャリーブチルアクリルアミドを高収率で製造し得る方法を提供することにある。
【０００４】
【課題を解決するための手段】
本発明者らは、上記の目的を達成するために鋭意検討した結果、反応時における重合や着色は、硫酸下で原料アクリロニトリル中に含まれてるＭＱ（メトキシハイドロキノン）などのような重合防止剤の分解生成物や原料中に含まれる鉄分を初めとする微量金属に起因していることが判った。また、本反応はキレート剤の共存下で順調に行うことができ、これにより重合防止剤の分解を抑制することができること、反応液からの結晶取得時に微量金属イオンの混入を軽減できること、さらには、反応液からターシャリーブチルアクリルアミドを晶析させる際にキレート剤を含むアルカリ水溶液を使用すると、ターシャリーブチルアクリルアミド結晶への微量金属イオンの混入阻止をより効果的にすることができること、等を見出した。本発明はこのような知見に基づいてなされたものである。
【０００５】
すなわち、本発明の一つは、ターシャリーブタノールとアクリロニトリルとを強酸存在下に反応せしめてターシャリーブチルアクリルアミドを製造する際に、該反応をキレート剤の共存下で行うことを特徴とするターシャリーブチルアクリルアミドの製造方法に関する。
【０００６】
本発明の他の一つは、ターシャリーブタノールとアクリロニトリルとを強酸およびキレート剤の共存下に反応せしめて得られた反応液を、キレート剤を含むアルカリ水溶液で中和処理してターシャリーブチルアクリルアミドを晶析させることを特徴とするターシャリーブチルアクリルアミドの製造方法に関する。
【０００７】
【発明の実施の形態】
以下、本発明を具体的に説明する。
本発明の方法において使用されるターシャリーブタノール、アクリロニトリル、強酸は、市販のものをそのまま用いることができる。また、必要に応じ水で希釈して用いてもよい。強酸としては、硫酸、燐酸、硝酸等が用いられるが、廃水処理などの観点から硫酸が好ましい。酸濃度は６５〜９８％、好ましくは７０〜８５％の範囲であるのがよい。
【０００８】
本発明の方法において使用されるキレート剤は、下記の一般式（１）で示されるアミノポリ燐酸および一般式（２）で示されるアミノポリカルボン酸である。
一般式（１） Ｒ１ Ｎ（ＣＨ２ ＰＯ３ ＭＭ’）２
〔式中、Ｒ１ は、水素、炭素数１〜４の直鎖または側鎖のアルキル基、ＣＨ２ ＰＯ３ ＭＭ’もしくはＣＨ２ ＣＨ２ ＮＲ２ ＣＨ２ ＰＯ３ ＭＭ’、ここでＲ２ は、ＣＨ２ ＰＯ３ ＭＭ’もしくはＣＨ２ ＣＨ２ Ｎ（ＣＨ２ ＰＯ３ ＭＭ’）２ 、Ｍ，Ｍ’は、水素またはアルカリ金属を示す〕
一般式（２） Ｒ３ Ｎ（ＣＨ２ ＣＯ２ Ｍ）２
〔式中、Ｒ３ は、水素、炭素数１〜４の直鎖または側鎖のアルキル基、ＣＨ２ ＣＯ２ ＭもしくはＣＨ２ ＣＨ２ ＮＲ４ ＣＨ２ ＣＯ２ Ｍ、ここでＲ４ は、ＣＨ ２ ＣＯ２ ＭもしくはＣＨ２ ＣＨ２ Ｎ（ＣＨ２ ＣＯ２ Ｍ）２ 、Ｍは、水素またはアルカリ金属を示す〕
これらのキレート剤を具体的に例示すると、一般式（１）で示されるアミノポリ燐酸としては、ＣＨ３ Ｎ（ＣＨ２ ＰＯ３ Ｈ２ ）２ 、Ｎ（ＣＨ２ ＰＯ３ Ｈ２ ）３ 、（（ＯＨ）２ ＰＯＣＨ２ ）２ ＮＣＨ２ ＣＨ２ Ｎ（ＣＨ２ ＰＯ３ Ｈ２ ）２ 、（（ＯＨ）２ ＰＯＣＨ２ ）２ ＮＣＨ２ ＣＨ２ Ｎ（ＣＨ２ ＰＯ３ Ｈ２ ）ＣＨ２ ＣＨ２ Ｎ（ＣＨ２ ＰＯ２ Ｈ２ ）２ 等の化合物である。
また、一般式（２）で示されるアミノポリカルボン酸としては、ＣＨ３ Ｎ（ＣＨ２ ＣＯＯＨ）２ 、Ｎ（ＣＨ２ ＣＯＯＨ）３ 、（（ＯＨ）ＣＯＣＨ２ ）２ ＮＣＨ２ ＣＨ２ Ｎ（ＣＨ２ ＣＯＯＨ）２ 、（（ＯＨ）ＣＯＣＨ２ ）２ ＮＣＨ２ ＣＨ２ Ｎ（ＣＨ２ ＣＯＯＨ）ＣＨ２ ＣＨ２ Ｎ（ＣＨ２ ＣＯＯＨ）２ 等の化合物である。
入手することの容易さの観点から、前記アミノポリ燐酸としてはエチレンジアミンテトラメチレンホスフォン酸（ＥＤＴＰ）、ジエチレントリアミンペンタメチレンホスフォン酸（ＤＴＰＰ）等、前記アミノポリカルボン酸としてはエチレンジアミン四酢酸（ＥＤＴＡ）、ジエチレントリアミン五酢酸（ＤＴＰＡ）、ニトリロ三酢酸（ＮＴＡ）、イミノ二酢酸（ＩＤＡ）等が好ましい。
また、これらのキレート剤は一種又は二種以上用いることができる。
【０００９】
本発明の方法は、次のようにして行うことができる。
反応器に強酸とキレート剤を入れ、これにターシャリーブタノールとアクリロニトリルを混合物の状態で、あるいは同時に添加したのち熟成反応を行う。原料の使用量は、アクロニトリル１モルに対して、ターシャリーブタノールが０．９〜１．５モル、好ましくは１〜１．２モルの範囲であること、また強酸が０．９〜１．５モル、好ましくは１〜１．３モルの範囲であることがよい。キレート剤は反応系に最初から添加することも、熟成反応時に添加することもできるが、原料アクリロニトリル中に含まれてる重合禁止剤に対する安定効果を高めることや反応液からの結晶取得時における微量金属イオンの混入阻止の観点から反応系に最初から添加するのが好ましい。キレート剤の添加量は、１０〜１０００ｐｐｍ、好ましくは５０〜５００ｐｐｍの範囲内で適宜選択すればよい。キレート剤としては、強酸中で溶解度が高いもの、たとえばエチレンジアミンテトラメチレンホスフォン酸、ジエチレントリアミンペンタメチレンホスフォン酸等を用いるのが特に好ましい。
【００１０】
また、ターシャリーブタノールとアクリロニトリルの添加は反応系内の温度が２０〜４５℃、好ましくは２５〜４０℃を保持されるようにして行うのがよい。添加時に系内の温度が４５℃より高く成り過ぎると生成物の着色を招いたり、突発的な重合が起こったりすることがある。また、２０℃より低過ぎると反応が進まず、反応熟成時間を長時間必要とするばかりでなく未反応原料が蓄積したりすることがある。熟成反応の温度は３０〜４５℃、好ましくは３５〜４０℃の範囲であることがよい。熟成時間は２〜２０時間、好ましくは４〜１５時間の範囲であることがよい。
【００１１】
熟成反応が終了後、反応液を水と混合してターシャリーブチルアクリルアミドの結晶を析出させ、分離して、目的物を単離する。この際、キレート剤の存在下、反応液にアルカリを加えて中和処理を行うことにより目的物をより効果的に単離することができる。
アルカリによる反応液の中和処理は、反応液を水と混合する前でも後でも、あるいは水との混合とアルカリによる中和の操作を同時に行うこともできる。発生する中和熱の除去を考慮すると、反応液と水とを混合した後にアルカリを加えるか、またはアルカリを含む水と反応液とを混合するのがよい。
【００１２】
結晶を析出させる時の温度は、２０〜５５℃、好ましくは２５〜４０℃の範囲で行うのがよい。温度が５５℃より高く成り過ぎるとターシャリーブチルアクリルアミドが熱重合を起こし易くなり、２０℃より低過ぎると結晶が微細となり、取得結晶中に副生する硫酸ナトリウムやアクリル酸などの不純物が多く混入し好ましくない。キレート剤の使用量は、１０〜１５００ｐｐｍ、好ましくは２０〜１０００ｐｐｍの範囲内で適宜選択すればよい。キレート剤としては、経済性、操作性がよいことからＥＤＴＡナトリウム塩、ＤＴＰＡナトリウム塩等を用いるのが特に好ましい。
【００１３】
反応液の中和処理に用いられるアルカリとしては、水酸化ナトリウム、水酸化カリウム、水酸化リチウム等のアルカリ金属水酸化物、炭酸ナトリウム、炭酸カリウム、炭酸リチウム等のアルカリ金属炭酸塩等が挙げられる。その使用量は強酸性を中和するに要する量で１当量前後がよく、中和後のｐＨが４〜９、好ましくは５〜８の範囲となるように使用するのがよい。アルカリ水溶液として用いる場合には、その濃度は１〜３５％、好ましくは１０〜２５％の範囲である。
析出した結晶は、分離、水洗した後、乾燥することによって高品質のターシャリーブチルアクリルアミドが得られる。
【００１４】
【実施例】
以下、実施例によって、本発明を具体的に説明するが、本発明はこの実施例のみに限定されるものではない。
【００１５】
実施例１
攪拌機、温度計、ジムロート冷却管、滴下ロートを備えた１０００ｃｃ円筒型フラスコに、工業用硫酸を希釈して得た８０％硫酸６０１．６ｇとＤＴＰＰ０．１ｇを仕込む。滴下ロートよりターシャリーブタノール３２６．１ｇとアクリロニトリル２１２ｇの混合液を、反応液の温度を４０℃以下に保持しながら滴下する。滴下終了後、反応液の温度を３５〜４０℃に保ち１０時間熟成する。
ついで、熟成反応液をＤＴＰＡ０．４１ｇを含む１４．５％苛性ソーダ水溶液１３５１．７ｇに、液温が４０℃を超えないようにしながら滴下し結晶を析出させた。析出した結晶を遠心分離器を用いて母液と分離し、水洗した後、７０℃で５時間乾燥して白色針状結晶ターシャリーブチルアクリルアミド４６２．３ｇを得た（アクリロニトリル基準収率：９１％）。この結晶に含まれている金属不純物は鉄イオンが１ｐｐｍ以下であり、結晶の色相はこの結晶を１０重量％メタノール溶液として測定した結果、ＡＰＨＡで１０であった。
【００１６】
実施例２
攪拌機、温度計、ジムロート冷却管、滴下ロートを備えた１０００ｃｃ円筒型フラスコに、工業用硫酸を希釈して得た８０％硫酸６０１．６ｇとＤＴＰＡ０．１ｇを仕込む。滴下ロートよりターシャリーブタノール３２６．１ｇとアクリロニトリル２１２ｇの混合液を、反応液の温度を４０℃以下に保持しながら滴下する。滴下終了後、反応液の温度を３５〜４０℃に保ち１０時間熟成する。
ついで、熟成反応液をＥＤＴＡ０．４３ｇを含む１４．５％苛性ソーダ水溶液１３５１．７ｇに、液温が４０℃を超えないようにしながら滴下し結晶を析出させた。析出した結晶を遠心分離器をもちいて母液と分離し、水洗した後、７０℃で５時間乾燥して白色針状結晶ターシャリーブチルアクリルアミド４６７．４ｇを得た（アクリロニトリル基準収率：９２％）。この結晶に含まれている金属不純物は鉄イオンが３ｐｐｍであり、結晶の色相はこの結晶を１０重量％メタノール溶液として測定した結果、ＡＰＨＡで２５であった。
【００１７】
実施例３〜６
キレート剤を変えたこと以外は実施例１と同様の方法で反応を行い、ターシャリーブチルアクリルアミドを得た。その結果は表１に示す。
比較例１
攪拌機、温度計、ジムロート冷却管、滴下ロートを備えた１０００ｃｃ円筒型フラスコに工業用硫酸を希釈して得た８０％硫酸６０１．６ｇを仕込む。滴下ロートよりターシャリーブタノール３２６．１ｇとアクリロニトリル２１２ｇの混合液を、反応液の温度を４０℃以下に保持しながら滴下する。滴下終了後、反応液の温度を３５〜４０℃に保ち１０時間熟成する。
ついで、熟成反応液を１４．５％苛性ソーダ水溶液１３５１．７ｇに、液温が４０℃を超えないようにしながら滴下し結晶を析出させた。析出した結晶を遠心分離器をもちいて母液と分離し、水洗した後、７０℃で５時間乾燥して白色針状結晶ターシャリーブチルアクリルアミド４６２．３ｇを得た（アクリロニトリル基準収率：９１％）。この結晶に含まれている金属不純物は鉄イオンが２５ｐｐｍであり、結晶の色相はこの結晶を１０重量％メタノール溶液として測定した結果、ＡＰＨＡで１００であった。
【００１９】
【発明の効果】
本発明の方法によれば、反応および目的物の結晶化の際に特定のキレート剤を使用することによって、反応時における重合を防止すると共に不純物が少なく着色のない高品質のターシャリーブチルアクリルアミドを高収率で製造することができる。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a method for producing tertiary butyl acrylamide.
Tertiary butyl acrylamide is a useful substance as a raw material for modifiers of acrylonitrile-based synthetic fibers, rubber chemicals, paints, and the like.
[0002]
[Prior art and problems]
Conventionally, as a method for producing tertiary butyl acrylamide, tertiary butanol and acrylonitrile are reacted in the presence of concentrated sulfuric acid, and the resulting reaction solution is added to water to crystallize and obtain tertiary butyl acrylamide. (Journal of the American Society, Vol. 73, No. 9, p. 4076 (1951)) or partial neutralization of the reaction mixture with an aqueous alkali solution to PH2-4, and carbonization of amides such as xylene. There is a method of extracting and separating with a hydrogen solvent (Japanese Patent Publication No. 43-8087). However, these methods have a problem that polymerization occurs during the reaction or the reaction solution is colored. Furthermore, the former method not only reduces the purity by mixing an acidic substance such as acrylic acid as a by-product into the target product tertiary butyl acrylamide during crystallization acquisition, but also uses the obtained tertiary butyl acrylamide. There is also a problem that the polymer produces an odor when polymerized. In addition, in order to obtain the separation, an expensive acid-resistant crystal precipitation tank or separator is required to perform crystal precipitation and separation under strongly acidic conditions. On the other hand, the latter method involves complicated steps for extracting and separating the reaction mixture while appropriately neutralizing the reaction mixture with an aqueous alkali solution in order to reduce the adverse effects of trace amounts of metal ions present in the raw materials. There was a problem in operation, such as needing.
[0003]
[Problems to be solved by the invention]
An object of the present invention is to solve these problems in the prior art, and a method for producing high-quality tertiary butyl acrylamide of high quality with less impurities and no coloration while preventing polymerization during the reaction is provided. To provide.
[0004]
[Means for Solving the Problems]
The present inventors have conducted intensive studies to achieve the above object. As a result, the polymerization and coloring during the reaction were carried out by using a polymerization inhibitor such as MQ (methoxyhydroquinone) contained in the raw material acrylonitrile under sulfuric acid. It was found that it was caused by trace metals such as decomposition products and iron contained in the raw materials. This reaction can be carried out smoothly in the presence of a chelating agent, whereby the decomposition of the polymerization inhibitor can be suppressed, and the contamination of trace metal ions during the acquisition of crystals from the reaction solution can be reduced. Found that the use of an alkaline aqueous solution containing a chelating agent when crystallizing tertiary butyl acrylamide from a reaction solution can more effectively prevent the entry of trace metal ions into tertiary butyl acrylamide crystals. Was. The present invention has been made based on such findings.
[0005]
That is, one of the present invention is to produce tertiary butyl acrylamide by reacting tertiary butanol and acrylonitrile in the presence of a strong acid, and performing the reaction in the presence of a chelating agent. The present invention relates to a method for producing butylacrylamide.
[0006]
Another aspect of the present invention is to provide a reaction solution obtained by reacting tertiary butanol and acrylonitrile in the presence of a strong acid and a chelating agent, and neutralizing the reaction solution with an aqueous alkali solution containing a chelating agent to form tertiary butyl acrylamide. And a process for producing tertiary butyl acrylamide.
[0007]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, the present invention will be described specifically.
As the tertiary butanol, acrylonitrile, and strong acid used in the method of the present invention, commercially available ones can be used as they are. Moreover, you may dilute with water as needed and use it. As the strong acid, sulfuric acid, phosphoric acid, nitric acid and the like are used, but sulfuric acid is preferable from the viewpoint of wastewater treatment. The acid concentration is in the range of 65 to 98%, preferably 70 to 85%.
[0008]
The chelating agent used in the method of the present invention is an aminopolyphosphoric acid represented by the following general formula (1) and an aminopolycarboxylic acid represented by the following general formula (2).
General formula (1) R 1 N (CH 2 PO 3 MM ′) 2
[In the formula, R 1 is hydrogen, a linear or branched alkyl group having 1 to 4 carbon atoms, CH 2 PO 3 MM ′ or CH 2 CH 2 NR 2 CH 2 PO 3 MM ′, wherein R 2 is , CH 2 PO 3 MM ′ or CH 2 CH 2 N (CH 2 PO 3 MM ′) 2 , M and M ′ represent hydrogen or an alkali metal]
General formula (2) R 3 N (CH 2 CO 2 M) 2
[Wherein, R 3 is hydrogen, a linear or branched alkyl group having 1 to 4 carbon atoms, CH 2 CO 2 M or CH 2 CH 2 NR 4 CH 2 CO 2 M, wherein R 4 is CH 2 CO 2 M or CH 2 CH 2 N (CH 2 CO 2 M) 2 , M represents hydrogen or an alkali metal]
When these chelating agents are specifically exemplified, as the aminopolyphosphoric acid represented by the general formula (1), CH 3 N (CH 2 PO 3 H 2 ) 2 , N (CH 2 PO 3 H 2 ) 3 , (( OH) 2 POCH 2) 2 NCH 2 CH 2 N (CH 2 PO 3 H 2) 2, ((OH) 2 POCH 2) 2 NCH 2 CH 2 N (CH 2 PO 3 H 2) CH 2 CH 2 N ( CH 2 PO 2 H 2 ) 2 and the like.
Examples of the aminopolycarboxylic acid represented by the general formula (2) include CH 3 N (CH 2 COOH) 2 , N (CH 2 COOH) 3 , ((OH) COCH 2 ) 2 NCH 2 CH 2 N (CH 2 COOH) 2, a ((OH) COCH 2) 2 NCH 2 CH 2 N (CH 2 COOH) CH 2 CH 2 N (CH 2 COOH) compound such 2.
From the viewpoint of easy availability, the aminopolyphosphoric acid is ethylenediaminetetramethylenephosphonic acid (EDTP), diethylenetriaminepentamethylenephosphonic acid (DTPP), etc., and the aminopolycarboxylic acid is ethylenediaminetetraacetic acid (EDTA). Diethylenetriaminepentaacetic acid (DTPA), nitrilotriacetic acid (NTA), iminodiacetic acid (IDA) and the like are preferred.
In addition, one or more of these chelating agents can be used.
[0009]
The method of the present invention can be performed as follows.
A strong acid and a chelating agent are charged into a reactor, and tertiary butanol and acrylonitrile are added in a mixed state or simultaneously, followed by a ripening reaction. The amount of the raw material used is 0.9 to 1.5 mol, preferably 1 to 1.2 mol, of tertiary butanol and 1 to 1.2 mol of strong acid, based on 1 mol of acronitrile. The range is 5 mol, preferably 1 to 1.3 mol. The chelating agent can be added to the reaction system from the beginning or at the time of the aging reaction.However, it can enhance the stabilizing effect on the polymerization inhibitor contained in the raw material acrylonitrile and trace metal when obtaining crystals from the reaction solution. It is preferable to add to the reaction system from the beginning from the viewpoint of preventing ion mixing. The addition amount of the chelating agent may be appropriately selected within the range of 10 to 1000 ppm, preferably 50 to 500 ppm. As the chelating agent, those having high solubility in strong acids, for example, ethylenediaminetetramethylenephosphonic acid, diethylenetriaminepentamethylenephosphonic acid, and the like are particularly preferably used.
[0010]
The addition of tertiary butanol and acrylonitrile is preferably carried out so that the temperature in the reaction system is maintained at 20 to 45 ° C, preferably 25 to 40 ° C. If the temperature in the system becomes too high at 45 ° C. at the time of addition, the product may be colored or sudden polymerization may occur. On the other hand, if the temperature is lower than 20 ° C., the reaction does not proceed, not only requiring a long time for the reaction aging but also accumulating unreacted raw materials. The temperature of the aging reaction is in the range of 30 to 45 ° C, preferably 35 to 40 ° C. The aging time is in the range of 2 to 20 hours, preferably 4 to 15 hours.
[0011]
After completion of the aging reaction, the reaction solution is mixed with water to precipitate tertiary butyl acrylamide crystals, which are separated and the target product is isolated. At this time, the target product can be more effectively isolated by performing a neutralization treatment by adding an alkali to the reaction solution in the presence of the chelating agent.
The neutralization of the reaction solution with an alkali can be performed before or after mixing the reaction solution with water, or the operation of mixing with water and neutralizing with an alkali can be performed simultaneously. In consideration of removal of the generated heat of neutralization, it is preferable to add an alkali after mixing the reaction solution and water, or to mix water containing the alkali with the reaction solution.
[0012]
The temperature at which the crystals are precipitated is preferably in the range of 20 to 55C, preferably 25 to 40C. If the temperature is higher than 55 ° C., tertiary butyl acrylamide tends to cause thermal polymerization. If the temperature is lower than 20 ° C., the crystals become finer, and impurities such as sodium sulfate and acrylic acid which are by-produced in the obtained crystals are mixed. But not preferred. The amount of the chelating agent used may be appropriately selected within the range of 10 to 1500 ppm, preferably 20 to 1000 ppm. As a chelating agent, it is particularly preferable to use sodium salt of EDTA, sodium salt of DTPA, or the like because of good economic efficiency and operability.
[0013]
Examples of the alkali used for the neutralization treatment of the reaction solution include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, and lithium hydroxide, and alkali metal carbonates such as sodium carbonate, potassium carbonate, and lithium carbonate. . The amount used is an amount required to neutralize the strong acidity and is preferably about 1 equivalent, and the pH after neutralization is preferably 4 to 9, preferably 5 to 8. When used as an aqueous alkaline solution, its concentration is in the range of 1 to 35%, preferably 10 to 25%.
The precipitated crystals are separated, washed with water, and dried to obtain high quality tertiary butyl acrylamide.
[0014]
【Example】
Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited to these Examples.
[0015]
Example 1
In a 1000 cc cylindrical flask equipped with a stirrer, thermometer, Dimroth condenser, and dropping funnel, 601.6 g of 80% sulfuric acid obtained by diluting industrial sulfuric acid and 0.1 g of DTPP are charged. A mixture of 326.1 g of tertiary butanol and 212 g of acrylonitrile is added dropwise from the dropping funnel while maintaining the temperature of the reaction solution at 40 ° C. or lower. After completion of the dropwise addition, the temperature of the reaction solution is kept at 35 to 40 ° C., and the mixture is aged for 10 hours.
Next, the ripening reaction solution was added dropwise to 1351.7 g of a 14.5% aqueous solution of caustic soda containing 0.41 g of DTPA while keeping the liquid temperature not exceeding 40 ° C. to precipitate crystals. The precipitated crystals were separated from the mother liquor using a centrifugal separator, washed with water, and dried at 70 ° C. for 5 hours to obtain 462.3 g of tertiary butyl acrylamide white needle crystals (acrylonitrile yield: 91%). . The metal impurities contained in the crystals contained 1 ppm or less of iron ions, and the hue of the crystals was determined to be 10 in APHA as a result of measuring the crystals as a 10% by weight methanol solution.
[0016]
Example 2
In a 1000 cc cylindrical flask equipped with a stirrer, thermometer, Dimroth condenser, and dropping funnel, 601.6 g of 80% sulfuric acid obtained by diluting industrial sulfuric acid and 0.1 g of DTPA are charged. A mixture of 326.1 g of tertiary butanol and 212 g of acrylonitrile is added dropwise from the dropping funnel while maintaining the temperature of the reaction solution at 40 ° C. or lower. After completion of the dropwise addition, the temperature of the reaction solution is kept at 35 to 40 ° C., and the mixture is aged for 10 hours.
Next, the ripening reaction solution was added dropwise to 1351.7 g of a 14.5% aqueous solution of caustic soda containing 0.43 g of EDTA while keeping the solution temperature not exceeding 40 ° C. to precipitate crystals. The precipitated crystals were separated from the mother liquor using a centrifugal separator, washed with water, and dried at 70 ° C. for 5 hours to obtain 467.4 g of tertiary butyl acrylamide white needle crystals (acrylonitrile yield: 92%). . The metal impurities contained in the crystals were 3 ppm of iron ions, and the hue of the crystals was 25 in APHA as a result of measuring the crystals as a 10% by weight methanol solution.
[0017]
Examples 3 to 6
The reaction was carried out in the same manner as in Example 1 except that the chelating agent was changed to obtain tertiary butyl acrylamide. The results are shown in Table 1.
Comparative Example 1
601.6 g of 80% sulfuric acid obtained by diluting industrial sulfuric acid is charged into a 1000 cc cylindrical flask equipped with a stirrer, a thermometer, a Dimroth condenser, and a dropping funnel. A mixed liquid of 326.1 g of tertiary butanol and 212 g of acrylonitrile is dropped from the dropping funnel while maintaining the temperature of the reaction solution at 40 ° C. or lower. After completion of the dropwise addition, the temperature of the reaction solution is kept at 35 to 40 ° C., and the mixture is aged for 10 hours.
Next, the ripening reaction solution was added dropwise to 1351.7 g of a 14.5% aqueous solution of caustic soda while keeping the solution temperature not exceeding 40 ° C. to precipitate crystals. The precipitated crystals were separated from the mother liquor using a centrifugal separator, washed with water and dried at 70 ° C. for 5 hours to obtain 462.3 g of tertiary butyl acrylamide white needle crystals (acrylonitrile yield: 91%). . The metal impurities contained in the crystal were iron ions at 25 ppm, and the hue of the crystal was 100 in APHA as a result of measuring the crystal as a 10% by weight methanol solution.
[0019]
【The invention's effect】
According to the method of the present invention, by using a specific chelating agent at the time of reaction and crystallization of the target substance, high-quality tertiary butyl acrylamide which prevents polymerization at the time of reaction and has less impurities and no coloring is obtained. It can be produced in high yield.
Claims (6)
一般式（１） Ｒ１ Ｎ（ＣＨ２ ＰＯ３ ＭＭ’）２
〔式中、Ｒ１ は、水素、炭素数１〜４の直鎖または側鎖のアルキル基、ＣＨ２ ＰＯ３ ＭＭ’もしくはＣＨ２ ＣＨ２ ＮＲ２ ＣＨ２ ＰＯ３ ＭＭ’、ここでＲ２ は、ＣＨ２ ＰＯ３ ＭＭ’もしくはＣＨ２ ＣＨ２ Ｎ（ＣＨ２ ＰＯ３ ＭＭ’）２ 、Ｍ，Ｍ’は、水素またはアルカリ金属を示す〕
一般式（２） Ｒ３ Ｎ（ＣＨ２ ＣＯ２ Ｍ）２
〔式中、Ｒ３ は、水素、炭素数１〜４の直鎖または側鎖のアルキル基、ＣＨ２ ＣＯ２ ＭもしくはＣＨ２ ＣＨ２ ＮＲ４ ＣＨ２ ＣＯ２ Ｍ、ここでＲ４ は、ＣＨ ２ ＣＯ２ ＭもしくはＣＨ２ ＣＨ２ Ｎ（ＣＨ２ ＣＯ２ Ｍ）２ 、Ｍは、水素またはアルカリ金属を示す〕The method for producing tertiary butyl acrylamide according to claim 1, wherein the chelating agent is an aminopolyphosphoric acid represented by the following general formula (1) and / or an aminopolycarboxylic acid represented by the following general formula (2).
General formula (1) R 1 N (CH 2 PO 3 MM ′) 2
[In the formula, R 1 is hydrogen, a linear or branched alkyl group having 1 to 4 carbon atoms, CH 2 PO 3 MM ′ or CH 2 CH 2 NR 2 CH 2 PO 3 MM ′, wherein R 2 is , CH 2 PO 3 MM ′ or CH 2 CH 2 N (CH 2 PO 3 MM ′) 2 , M and M ′ represent hydrogen or an alkali metal]
General formula (2) R 3 N (CH 2 CO 2 M) 2
[Wherein, R 3 is hydrogen, a linear or branched alkyl group having 1 to 4 carbon atoms, CH 2 CO 2 M or CH 2 CH 2 NR 4 CH 2 CO 2 M, wherein R 4 is CH 2 CO 2 M or CH 2 CH 2 N (CH 2 CO 2 M) 2 , M represents hydrogen or an alkali metal]
一般式（１） Ｒ１ Ｎ（ＣＨ２ ＰＯ３ ＭＭ’）２
〔式中、Ｒ１ は、水素、炭素数１〜４の直鎖または側鎖のアルキル基、ＣＨ２ ＰＯ３ ＭＭ’もしくはＣＨ２ ＣＨ２ ＮＲ２ ＣＨ２ ＰＯ３ ＭＭ’、ここでＲ２ は、ＣＨ２ ＰＯ３ ＭＭ’もしくはＣＨ２ ＣＨ２ Ｎ（ＣＨ２ ＰＯ３ ＭＭ’）２ 、Ｍ，Ｍ’は、水素またはアルカリ金属を示す〕
一般式（２） Ｒ３ Ｎ（ＣＨ２ ＣＯ２ Ｍ）２
〔式中、Ｒ３ は、水素、炭素数１〜４の直鎖または側鎖のアルキル基、ＣＨ２ ＣＯ２ ＭもしくはＣＨ２ ＣＨ２ ＮＲ４ ＣＨ２ ＣＯ２ Ｍ、ここでＲ４ は、ＣＨ ２ ＣＯ２ ＭもしくはＣＨ２ ＣＨ２ Ｎ（ＣＨ２ ＣＯ２ Ｍ）２ 、Ｍは、水素またはアルカリ金属を示す〕The method for producing tertiary butyl acrylamide according to claim 4, wherein the chelating agent is an aminopolyphosphoric acid represented by the following general formula (1) and / or an aminopolycarboxylic acid represented by the following general formula (2).
General formula (1) R 1 N (CH 2 PO 3 MM ′) 2
[In the formula, R 1 is hydrogen, a linear or branched alkyl group having 1 to 4 carbon atoms, CH 2 PO 3 MM ′ or CH 2 CH 2 NR 2 CH 2 PO 3 MM ′, wherein R 2 is , CH 2 PO 3 MM ′ or CH 2 CH 2 N (CH 2 PO 3 MM ′) 2 , M and M ′ represent hydrogen or an alkali metal]
General formula (2) R 3 N (CH 2 CO 2 M) 2
[Wherein, R 3 is hydrogen, a linear or branched alkyl group having 1 to 4 carbon atoms, CH 2 CO 2 M or CH 2 CH 2 NR 4 CH 2 CO 2 M, wherein R 4 is CH 2 CO 2 M or CH 2 CH 2 N (CH 2 CO 2 M) 2 , M represents hydrogen or an alkali metal]
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30329595A JP3586503B2 (en) | 1995-10-30 | 1995-10-30 | Method for producing tertiary butyl acrylamide |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30329595A JP3586503B2 (en) | 1995-10-30 | 1995-10-30 | Method for producing tertiary butyl acrylamide |
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| Publication Number | Publication Date |
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| JPH09124568A JPH09124568A (en) | 1997-05-13 |
| JP3586503B2 true JP3586503B2 (en) | 2004-11-10 |
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| JP30329595A Expired - Lifetime JP3586503B2 (en) | 1995-10-30 | 1995-10-30 | Method for producing tertiary butyl acrylamide |
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| JP2005343845A (en) * | 2004-06-04 | 2005-12-15 | Hakuto Co Ltd | Polymerization inhibitor and method for inhibiting polymerization of acrylonitrile |
| JP4582641B2 (en) * | 2005-03-29 | 2010-11-17 | 伯東株式会社 | Polymerization inhibitor and method for inhibiting polymerization of acrylonitrile |
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