JP2691020B2 - Method for producing Nt-butyl acrylamide - Google Patents
Method for producing Nt-butyl acrylamideInfo
- Publication number
- JP2691020B2 JP2691020B2 JP1129547A JP12954789A JP2691020B2 JP 2691020 B2 JP2691020 B2 JP 2691020B2 JP 1129547 A JP1129547 A JP 1129547A JP 12954789 A JP12954789 A JP 12954789A JP 2691020 B2 JP2691020 B2 JP 2691020B2
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- reaction
- producing
- water
- acrylonitrile
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【発明の詳細な説明】 (産業上の利用分野) 本発明は、有機ゴム薬品や医薬品の原材料として有用
なモノ3級アルキルアミンの中間体であるN−t−ブチ
ルアクリルアミドの製造法に関するものである。TECHNICAL FIELD The present invention relates to a method for producing Nt-butylacrylamide, which is an intermediate of a mono-tertiary alkylamine useful as a raw material for organic rubber chemicals and pharmaceuticals. is there.
(従来技術および発明が解決しようとする課題) 従来、N−t−ブチルアクリルアミドの製造方法とし
て、アクリロニトリルとt−ブチルアルコールを酢酸溶
媒中で濃硫酸の存在下において40℃で反応させる方法
(J.Amer.Chem.Soc.73,(9),4076(1951))やアク
リロニトリルとt−ブチルアルコールをメタノール又は
エタノール溶媒中で濃硫酸の存在下において40〜60℃で
反応させる方法(特公昭47-51329)等が知られている。(Prior Art and Problems to be Solved by the Invention) Conventionally, as a method for producing Nt-butylacrylamide, a method of reacting acrylonitrile and t-butyl alcohol in an acetic acid solvent at 40 ° C. in the presence of concentrated sulfuric acid (J Amer. Chem. Soc. 73 , (9), 4076 (1951)) or acrylonitrile and t-butyl alcohol in a methanol or ethanol solvent at 40 to 60 ° C in the presence of concentrated sulfuric acid (JP-B-47). -51329) etc. are known.
しかしながらこれらの方法では、高温で反応したり、
あるいは反応が不均一で発熱が突発的なことから温度制
御が困難であるため温度が上昇したりする。そのため、
生成物中に副反応によって生じた変性物質及び重合体物
質が混入し、得られたN−t−ブチルアクリルアミドの
品位は好ましいものではない。However, in these methods, reaction at high temperature,
Alternatively, the temperature rises because it is difficult to control the temperature because the reaction is non-uniform and the heat generation is sudden. for that reason,
The modified substance and the polymer substance produced by the side reaction are mixed in the product, and the quality of the obtained Nt-butylacrylamide is not preferable.
本発明は、このような不均一で発熱が突発的な反応を
抑制し、かつ、低温で反応させることによって、高品位
のN−t−ブチルアクリルアミドを製造することを目的
とするものである。An object of the present invention is to produce a high-quality Nt-butyl acrylamide by suppressing such a heterogeneous and sudden heat generation reaction and reacting at a low temperature.
(課題を解決するための手段) 本発明は、t−ブチルアルコールとアクリロニトリル
とを硫酸の存在下で反応させてN−t−ブチルアクリル
アミドを製造する方法において、溶媒として酢酸−水の
混合溶媒を使用すると共に、反応系内の水のモル濃度を
0.7〜4.5モル/l(リットル)とすることを特徴とするN
−t−ブチルアクリルアミドの製造法を提供する。水の
モル濃度がこの範囲より多い場合には反応速度が小さく
なり経済性が悪くなる傾向を有する。又、この範囲より
少ない場合には反応系の粘度上昇が起こると共に、発熱
が突発的となるため、反応温度の制御が困難となり、得
られたN−t−ブチルアクリルアミドの品位が悪くな
る。混合溶媒量については、通常、原料系(アクリロニ
トリルとt−ブチルアルコールの合計)の0.4〜1.0倍
(重量比)が適当であるがこの範囲を少々外れても本発
明の実施は可能である。硫酸添加量はアクリロニトリル
に対して、通常モル比で0.5倍モル以上であり、1.0倍モ
ル程度が好ましい。(Means for Solving the Problem) The present invention is a method for producing Nt-butylacrylamide by reacting t-butyl alcohol and acrylonitrile in the presence of sulfuric acid, and a mixed solvent of acetic acid-water is used as a solvent. As well as using, the molar concentration of water in the reaction system
N characterized by being 0.7 to 4.5 mol / l (liter)
A method for producing -t-butyl acrylamide is provided. If the molar concentration of water is higher than this range, the reaction rate tends to be low and the economy tends to be poor. On the other hand, when the amount is less than this range, the viscosity of the reaction system increases and the heat generation suddenly occurs, so that it becomes difficult to control the reaction temperature and the quality of the obtained Nt-butylacrylamide deteriorates. The amount of the mixed solvent is usually 0.4 to 1.0 times (weight ratio) of the raw material system (total of acrylonitrile and t-butyl alcohol), but the present invention can be carried out even if it is out of this range. The amount of sulfuric acid added is usually 0.5 times or more, and preferably about 1.0 times the molar ratio of acrylonitrile.
t−ブチルアルコールの好ましい使用量は、アクリロ
ニトリルに対するモル比が0.9以上であり特に0.9〜1.3
倍モルが好ましい。t−ブチルアルコールの使用量がこ
の範囲より多い場合、特に不都合はないが経済性が悪く
なるので好ましくない。又、t−ブチルアルコールの使
用量がこの範囲より少ない場合にはアクリロニトリルの
変性反応が伴い、生成変性物質がN−t−ブチルアクリ
ルアミドに混入してくるので好ましくない。The preferable amount of t-butyl alcohol used is such that the molar ratio to acrylonitrile is 0.9 or more, and particularly 0.9 to 1.3.
Double molar is preferred. When the amount of t-butyl alcohol used is more than this range, there is no particular inconvenience, but the economical efficiency is deteriorated, which is not preferable. On the other hand, if the amount of t-butyl alcohol used is less than this range, the modification reaction of acrylonitrile will accompany and the resulting modified substance will be mixed into Nt-butyl acrylamide, which is not preferable.
反応温度は、−30〜40℃であり特に−10〜30℃が好ま
しい。反応温度がこの範囲より高い場合には副反応によ
って生じた変性物質及び重合体物質が、N−t−ブチル
アクリルアミドに混入してくるため好ましくない。又、
反応温度がこの範囲より低い場合には特に不都合はない
が反応速度が小さくなるため経済性が悪くなる。The reaction temperature is -30 to 40 ° C, particularly preferably -10 to 30 ° C. When the reaction temperature is higher than this range, the modifying substance and the polymer substance generated by the side reaction are mixed in Nt-butylacrylamide, which is not preferable. or,
When the reaction temperature is lower than this range, there is no particular inconvenience, but the reaction rate becomes small and the economy becomes poor.
本発明における反応の反応方式としては、回分式、連
続方式いずれを用いても目的を達成できる。As the reaction system of the reaction in the present invention, either the batch system or the continuous system can be used to achieve the object.
(作用) 本反応の反応機構は十分定かではないが、下記に示す
ごとく推定される。(Action) Although the reaction mechanism of this reaction is not completely clear, it is estimated as shown below.
反応が不均一で発熱が突発的になったり、往々にして
暴発的となったりする原因としては、N−t−ブチルア
クリルアミドの硫酸付加物の生成により反応系の粘度
が、極めて粘稠になることと、t−ブチルアルコール硫
酸の複合体の濃度の制御が、極めて難しいことによる。
そのため、溶媒による効果が、重要な原因を占めている
と考えられる。この知見から、酢酸−水の混合溶媒中で
反応を行うことによってN−t−ブチルアクリルアミド
の硫酸付加物の生成が抑制されるため反応系の粘度が上
昇せず、さらに、(2)の反応が平衡反応であることに
より反応の制御が極めて容易となったと考えられる。 The reason why the reaction is non-uniform and the heat generation suddenly occurs or is often violent is that the viscosity of the reaction system becomes extremely viscous due to the formation of a sulfuric acid adduct of N-t-butylacrylamide. It is extremely difficult to control the concentration of the complex of t-butyl alcohol sulfuric acid.
Therefore, it is considered that the effect of the solvent occupies an important cause. From this finding, the reaction in a mixed solvent of acetic acid-water suppresses the formation of a sulfuric acid adduct of Nt-butylacrylamide, so that the viscosity of the reaction system does not increase, and further, the reaction of (2) It is considered that the control of the reaction became extremely easy because of the equilibrium reaction.
(発明の効果と実施例) 本発明の方法によれば、反応での温度制御が極めて簡
単に行え、しかも、低温で反応が行えるため、副反応に
よる変性物質及び重合体物質が生じにくい。そのため、
目的とするN−t−ブチルアクリルアミドは、高品位の
ものを得ることができるので、本発明方法は工業的に非
常に有用である。(Effects and Examples of the Invention) According to the method of the present invention, the temperature control in the reaction can be performed very easily, and further, the reaction can be performed at a low temperature, so that the modified substance and the polymer substance due to the side reaction are unlikely to occur. for that reason,
Since the target Nt-butylacrylamide can be obtained in high quality, the method of the present invention is industrially very useful.
ここに云う高品位のN−t−ブチルアクリルアミドと
は、高速液体クロマトグラフイで分析した場合、その純
度が99.6%以上のものを指しており、99.9%以上のもの
が特に好ましい。The high-quality Nt-butylacrylamide referred to herein means that the purity thereof is 99.6% or more when analyzed by high performance liquid chromatography, and 99.9% or more is particularly preferable.
以下、本発明を実施例によって更に詳細に説明する
が、本発明はこれら実施例により何ら制限されるもので
はない。Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.
実施例1 3lの内容積を有するガラス製容器中に、アクリロニト
リル531g(10モル)、t−ブチルアルコール743g(10モ
ル)、酢酸741g水101g(2.4モル/l)を仕込む。この中
に、98%硫酸1010gを反応温度を25℃に保ちながら約10
時間かけて撹拌下に徐々に滴下した。滴下終了後の反応
液の粘度を20℃で測定したところ、48cpsであった。
又、反応液を高速液体クロマトグラフイで分析し、反応
収率を計算したところ、t−ブチルアルコールベースで
95%であった。この反応液を多量の氷水中に徐々に注
ぎ、撹拌してN−t−ブチルアクリルアミドを析出せし
めた。析出した結晶を濾過し、水洗した。次に得られた
結晶を高速液体クロマトグラフイで分析したところ、純
度は99.9%であり、非常に高品位のものであった。Example 1 A glass container having an inner volume of 3 l was charged with 531 g (10 mol) of acrylonitrile, 743 g (10 mol) of t-butyl alcohol, 741 g of acetic acid and 101 g (2.4 mol / l) of water. In this, 1010 g of 98% sulfuric acid was added to about 10 while keeping the reaction temperature at 25 ° C.
The solution was gradually added dropwise with stirring over time. The viscosity of the reaction solution after the dropping was measured at 20 ° C. and found to be 48 cps.
The reaction liquid was analyzed by high performance liquid chromatography and the reaction yield was calculated.
95%. The reaction solution was gradually poured into a large amount of ice water and stirred to precipitate Nt-butylacrylamide. The precipitated crystals were filtered and washed with water. Next, when the obtained crystals were analyzed by high performance liquid chromatography, the purity was 99.9%, which was a very high quality.
実施例2 水101gの代わりに140g(3.7モル/l)を添加して行っ
た他は、実施例1と同様に行った。Example 2 Example 1 was repeated except that 140 g (3.7 mol / l) was added instead of 101 g water.
結果:表1に記載 実施例3 アクリロニトリル531gの代わりに、584g(11モル)を
用いた他は、実施例1と同様に行った。Results: As shown in Table 1. Example 3 The procedure of Example 1 was repeated, except that 584 g (11 mol) was used instead of 531 g of acrylonitrile.
結果:表1に記載 実施例4 反応温度を25℃の代わりに、−10℃で行った他は、実
施例1と同様に行った。Results: described in Table 1 Example 4 The same procedure as in Example 1 was carried out except that the reaction temperature was -10 ° C instead of 25 ° C.
結果:表1に記載 実施例5 アクリロニトリル531gの代わりに483g(9.1モル)を
用い、水101gの代わりに42g(1.0モル/l)を添加し、反
応温度を25℃の代わりに35℃で行った他は実施例1と同
様に行った。Result: As shown in Table 1. Example 5 483 g (9.1 mol) was used instead of 531 g of acrylonitrile, 42 g (1.0 mol / l) was added instead of 101 g of water, and the reaction temperature was 35 ° C instead of 25 ° C. Otherwise, the same procedure as in Example 1 was carried out.
結果:表1に記載 実施例6 反応温度を25℃の代わりに、50℃で行った他は、実施
例1と同様に行った。Results: As shown in Table 1. Example 6 The same procedure as in Example 1 was carried out except that the reaction temperature was 50 ° C instead of 25 ° C.
結果:表1に記載 実施例7 アクリロニトリル531gの代わりに605g(11.4モル)を
用いた他は、実施例1と同様に行った。Results: As shown in Table 1. Example 7 The same procedure as in Example 1 was carried out except that 605 g (11.4 mol) was used instead of 531 g of acrylonitrile.
結果:表1に記載 比較例1 水を添加しないで、酢酸741gの代わりに酢酸842gを用
いて実施例1と同様に行った。しかし、硫酸添加中に反
応が突発的におこり、反応温度を25℃に制御することが
できなかった。Results: As shown in Table 1 Comparative Example 1 The same procedure as in Example 1 was carried out without adding water and using 842 g of acetic acid instead of 741 g of acetic acid. However, the reaction temperature could not be controlled at 25 ℃ because the reaction suddenly occurred during the addition of sulfuric acid.
比較例2 水を添加しないで、反応温度を25℃の代わりに40℃で
行った他は実施例1と同様に行った。Comparative Example 2 The procedure of Example 1 was repeated except that water was not added and the reaction temperature was 40 ° C instead of 25 ° C.
結果:表1に記載 比較例3 水を添加しないで、反応温度を25℃の代わりに50℃で
行った他は実施例1と同様に行った。Results: described in Table 1 Comparative Example 3 The procedure of Example 1 was repeated except that water was not added and the reaction temperature was 50 ° C instead of 25 ° C.
結果:表1に記載 比較例4 水を添加しないで、酢酸741gの代わりにエチルアルコ
ール501gを用いておこなった他は、実施例1と同様に行
った。Results: described in Table 1 Comparative Example 4 The same procedure as in Example 1 was carried out except that 501 g of ethyl alcohol was used instead of 741 g of acetic acid without adding water.
結果:表1に記載 比較例5 水を添加しないで、酢酸741gの代わりにエチルアルコ
ール501gを用い、反応温度を25℃の代わりに50℃で行っ
た他は、実施例1と同様に行った。Results: described in Table 1 Comparative Example 5 The same procedure as in Example 1 was repeated except that 501 g of ethyl alcohol was used instead of 741 g of acetic acid and the reaction temperature was 50 ° C. instead of 25 ° C. without adding water. .
結果:表1に記載 比較例6 アクリロニトリル1115g(21モル)、t−ブチルアル
コール520g(7モル)、98%硫酸140gを仕込み、撹拌し
ながら反応温度80℃で3時間反応させた。Results: As shown in Table 1 Comparative Example 6 Acrylonitrile (1115 g, 21 mol), t-butyl alcohol (520 g, 7 mol) and 98% sulfuric acid (140 g) were charged and reacted at a reaction temperature of 80 ° C. for 3 hours while stirring.
結果:表1に記載 比較例7 水101gの代わりに、8g(0.2モル/l)を添加して行っ
た他は、実施例1と同様に行った。Results: described in Table 1 Comparative Example 7 The same procedure as in Example 1 was performed except that 8 g (0.2 mol / l) was added instead of 101 g of water.
結果:表1に記載 比較例8 アクリロニトリルを531gを代わりに483g(9.1モル)
用い、水を101gの代わりに21.0g(0.5モル/l)添加し、
反応温度を25℃の代わりに35℃とした以外は実施例1と
同様に行った。Results: described in Table 1 Comparative Example 8 483 g (9.1 mol) of acrylonitrile instead of 531 g
21.0 g (0.5 mol / l) of water was added instead of 101 g,
Example 1 was repeated except that the reaction temperature was 35 ° C instead of 25 ° C.
結果:表1に記載 実施例(7例)、比較例(8例)を一覧表に整理した
ものが表1である。Results: Listed in Table 1 Table 1 is a list of Examples (7 cases) and Comparative Examples (8 cases).
実施例1〜7と比較例1〜8の結果より、本願発明の
酢酸−水混合溶媒の効果が立証されている。なお酢酸溶
媒の場合、低温反応では反応温度の制御が困難となり
(反応暴走)、エタノール溶媒の場合、低温反応では反
応速度が著しく遅くなり、共に工業的には実用性がな
い。ここに云う低温反応とは概ね30℃以下での反応を指
す。The results of Examples 1 to 7 and Comparative Examples 1 to 8 prove the effect of the acetic acid-water mixed solvent of the present invention. In the case of an acetic acid solvent, it is difficult to control the reaction temperature in a low temperature reaction (reaction runaway), and in the case of an ethanol solvent, the reaction rate becomes extremely slow in a low temperature reaction, both of which are not industrially practical. The low temperature reaction mentioned here refers to a reaction at about 30 ° C. or lower.
Claims (3)
とを硫酸の存在下で反応させてN−t−ブチルアクリル
アミドを製造する方法において、溶媒として酢酸−水の
混合溶媒を使用すると共に、反応系内の水のモル濃度を
0.7〜4.5モル/l(リットル)とすることを特徴とするN
−t−ブチルアクリルアミドの製造法。1. A method for producing N-t-butylacrylamide by reacting t-butyl alcohol with acrylonitrile in the presence of sulfuric acid, wherein a mixed solvent of acetic acid-water is used as a solvent, and The molarity of water
N characterized by being 0.7 to 4.5 mol / l (liter)
-Method for producing t-butyl acrylamide.
コールのモル比が0.9以上である請求項1記載のN−t
−ブチルアクリルアミドの製造法。2. The Nt according to claim 1, wherein the molar ratio of t-butyl alcohol to acrylonitrile is 0.9 or more.
-Method for producing butyl acrylamide.
請求項2記載のN−t−ブチルアクリルアミドの製造
法。3. The method for producing Nt-butylacrylamide according to claim 1 or 2, wherein the reaction temperature is -30 to 40 ° C.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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JP1129547A JP2691020B2 (en) | 1989-05-23 | 1989-05-23 | Method for producing Nt-butyl acrylamide |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP1129547A JP2691020B2 (en) | 1989-05-23 | 1989-05-23 | Method for producing Nt-butyl acrylamide |
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Publication Number | Publication Date |
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JPH02306948A JPH02306948A (en) | 1990-12-20 |
JP2691020B2 true JP2691020B2 (en) | 1997-12-17 |
Family
ID=15012210
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JP1129547A Expired - Fee Related JP2691020B2 (en) | 1989-05-23 | 1989-05-23 | Method for producing Nt-butyl acrylamide |
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JP (1) | JP2691020B2 (en) |
Family Cites Families (1)
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US4868310A (en) * | 1986-08-04 | 1989-09-19 | Rohm And Haas Company | Process for preparing isothiazolones |
-
1989
- 1989-05-23 JP JP1129547A patent/JP2691020B2/en not_active Expired - Fee Related
Non-Patent Citations (1)
Title |
---|
J.Amer.Chem.Soc.,Vol.73,No.9,(1951),P.4076 |
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