JP2619527B2 - Method for stabilizing N-vinylacetamide - Google Patents
Method for stabilizing N-vinylacetamideInfo
- Publication number
- JP2619527B2 JP2619527B2 JP9418989A JP9418989A JP2619527B2 JP 2619527 B2 JP2619527 B2 JP 2619527B2 JP 9418989 A JP9418989 A JP 9418989A JP 9418989 A JP9418989 A JP 9418989A JP 2619527 B2 JP2619527 B2 JP 2619527B2
- Authority
- JP
- Japan
- Prior art keywords
- nva
- distillation
- salt
- present
- stabilizer
- 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.)
- Expired - Fee Related
Links
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【発明の詳細な説明】 （１）産業上の利用分野 本発明はＮ−ビニルアセトアミド（以下「NVA」と略
す）の安定化方法に関する。更に詳しくはNVAの貯蔵
時、蒸留精製時、または反応時等に安定化剤を添加して
NVAの変質を防止する方法に関する。NVAは、ポリビニル
アミンをはじめとする水溶性ポリマーの原料、あるいは
タウリン、システアミン等の有機薬品の中間原料として
有用であることが知られている。The present invention relates to a method for stabilizing N-vinylacetamide (hereinafter abbreviated as “NVA”). More specifically, a stabilizer is added during storage, purification by distillation, or reaction of NVA.
It relates to a method for preventing the deterioration of NVA. NVA is known to be useful as a raw material for water-soluble polymers such as polyvinylamine, or as an intermediate raw material for organic chemicals such as taurine and cysteamine.
（２）従来の技術 NVAは、水溶性ポリマーを与える重合性モノマーとし
て、また、有機薬品の中間原料として有用なものであり
（たとえば米国特許第4018826号公報、特開昭61-191671
号、同61-282354号）、また、その製造法も種々の提案
がある（たとえばジャーナル・オブ・アメリカン・ケミ
カル・ソサエティー第96巻,5996頁,1976年，特開昭55-1
53754号）。しかし、NVAは、貯蔵時、蒸留精製時、ある
いは反応時にその一部が変質し、損失を招きやすいこと
が知られている。(2) Prior art NVA is useful as a polymerizable monomer to give a water-soluble polymer and as an intermediate material for organic chemicals (for example, US Pat. No. 4,018,826, JP-A-61-191671).
No. 61-282354), and various methods for producing the same have been proposed (for example, Journal of American Chemical Society, Vol. 96, p. 5996, 1976, JP-A-55-1).
53754). However, it is known that NVA partially deteriorates during storage, distillation and purification, or during reaction, and is likely to cause loss.
（３）発明が解決しようとする課題 本発明は、上記実状に鑑み、貯蔵時、蒸留精製時、あ
るいは反応時等のNVAの変質による損失を防止するため
の簡便な方法の提供を目的とする。(3) Problems to be Solved by the Invention The present invention has been made in view of the above circumstances, and aims to provide a simple method for preventing loss due to deterioration of NVA during storage, distillation and purification, or during reaction. .
（４）課題を解決するための手段 本発明の目的は、本発明の方法に従ってNVA、あるい
はその溶液またはその分散液に安定化剤を添加すること
により達成される。(4) Means for Solving the Problems The object of the present invention is achieved by adding a stabilizer to NVA or a solution or dispersion thereof according to the method of the present invention.
すなわち本発明により、NVAに安定化剤を添加するこ
とでNVAの安定化方法が提供される。That is, the present invention provides a method for stabilizing NVA by adding a stabilizer to NVA.
NVAは貯蔵時、蒸留精製時、あるいは反応時等に熱、
混在する不純物、溶媒、分散媒等の作用により一部変質
する傾向がある。本発明者等は、NVAの変質防止方法に
つき鋭意検討を重ねた結果、本発明において特定する安
定化剤を添加した場合にNVAの安定化が図れることを見
いだし本発明を完成するに至った。NVA is heated during storage, distillation and purification, or during reaction.
It is liable to partially change due to the action of mixed impurities, solvent, dispersion medium and the like. The present inventors have conducted intensive studies on a method for preventing the deterioration of NVA, and as a result, have found that NVA can be stabilized when the stabilizer specified in the present invention is added, and have completed the present invention.
本発明において対象となるNVAはいかなる製法による
かは問わないが、たとえばアセトアルデヒドとアセトア
ミドの反応で得られるエチリデンビスアセトアミドの熱
分解（特開昭61-106546号）、Ｎ−（α−アルコキシエ
チル）アセトアミドの熱分解（特開昭50-76015号）等に
よって合成される。The NVA of the present invention may be prepared by any method, for example, thermal decomposition of ethylidene bisacetamide obtained by reaction of acetaldehyde and acetamide (JP-A-61-106546), N- (α-alkoxyethyl) It is synthesized by thermal decomposition of acetamide (JP-A-50-76015).
本発明においてNVAの安定化剤として用いられる化合
物としては、ジフェニルアミン、トリエチルアミン、α
−ナフチルアミン、β−ナフチルアミン、フェニルナフ
チルアミン、N,N′−ジ−β−ナフチル−ｐ−フェニレ
ンジアミン、フェノチアジン等の有機アミン化合物；炭
酸ナトリウム、炭酸カルシウム、炭酸水素ナトリウム、
リン酸カリウム、リン酸ナトリウム、リン酸水素二カリ
ウム、亜リン酸ナトリウム、亜リン酸カリウム、炭酸ア
ンモニウム、リン酸アンモニウム等の、アルカリ金属ま
たはアルカリ土類金属の弱酸塩もしくは弱酸水素塩ある
いは弱酸のアンモニウム塩類であって、該塩の水溶液が
アルカリ性を示す無機塩類；酢酸ナトリウム、酢酸カリ
ウム、酢酸マグネシウム、酢酸アンモニウム、プロピオ
ン酸ナトリウム、安息香酸ナトリウム、安息香酸カリウ
ム、ナトリウムフェノラート等の有機弱酸のアルカリ金
属塩、アルカリ土類金属塩またはアンモニウム塩等が挙
げられる。Compounds used as stabilizers for NVA in the present invention include diphenylamine, triethylamine, α
Organic amine compounds such as naphthylamine, β-naphthylamine, phenylnaphthylamine, N, N′-di-β-naphthyl-p-phenylenediamine, phenothiazine; sodium carbonate, calcium carbonate, sodium hydrogen carbonate,
Potassium phosphate, sodium phosphate, dipotassium hydrogen phosphate, sodium phosphite, potassium phosphite, ammonium carbonate, ammonium phosphate, etc. Ammonium salts, inorganic salts in which an aqueous solution of the salt shows alkalinity; alkalis of organic weak acids such as sodium acetate, potassium acetate, magnesium acetate, ammonium acetate, sodium propionate, sodium benzoate, potassium benzoate and sodium phenolate Examples thereof include metal salts, alkaline earth metal salts, and ammonium salts.
これらの安定化剤の使用量は、通常NVAに対して10〜5
0000ppm、好ましくは100〜10000ppmの範囲であり、使用
量が少なすぎるとNVAの変質を十分に抑制できず、また
多すぎてもその効果は変わらないので経済的でない。上
記の使用量の範囲で２種以上の安定化剤を併用すること
も可能である。The amount of these stabilizers used is usually 10 to 5 with respect to NVA.
The amount is in the range of 0000 ppm, preferably 100 to 10,000 ppm. If the amount is too small, the deterioration of NVA cannot be sufficiently suppressed, and if the amount is too large, the effect does not change and it is not economical. It is also possible to use two or more kinds of stabilizers in combination within the above range.
本発明の安定化剤は、NVAの貯蔵時、蒸留精製時、あ
るいは反応時等に適宜添加することによりその目的が達
成される。The object of the present invention is achieved by adding the stabilizer of the present invention appropriately during storage of NVA, during purification by distillation, or during reaction.
（５）実施例 以下、実施例により本発明を更に詳しく説明するが、
本発明はこれらの実施例のみに限定されないことは言う
までもない。(5) Examples Hereinafter, the present invention will be described in more detail with reference to Examples.
It goes without saying that the present invention is not limited to only these examples.
実施例１ Ｎ−（α−メトキシエチル）アセトアミドの熱分解に
より得られたNVA（純度85.5％）200g及び酢酸ナトリウ
ム0.5gを内容積500mlのナス型フラスコに入れ、浴温110
℃、圧力5.5mmHgで減圧蒸留した。蒸留に要した時間は
約1.5時間であった。留出温度87.5℃〜90.5℃の留分15
9.4gが得られ、ガスクロマトグラフィーによる分析では
純度99.5％のNVAであった。蒸留収率は92.8％であっ
た。Example 1 200 g of NVA (purity: 85.5%) obtained by thermal decomposition of N- (α-methoxyethyl) acetamide and 0.5 g of sodium acetate were put into a 500 ml eggplant type flask having a bath temperature of 110 ml.
Vacuum distillation was performed at 5.5 ° C. and a pressure of 5.5 mmHg. The time required for the distillation was about 1.5 hours. Distillate 15 with a distillation temperature of 87.5 to 90.5 ° C
9.4 g were obtained, and the purity of the NVA was 99.5% as analyzed by gas chromatography. The distillation yield was 92.8%.
比較例１ 実施例１と同じ条件でNVA（純度85.5％）200gを、安
定化剤を加えずに蒸留した。３時間加熱を続けたが、留
分は110.5gに過ぎなかった。ガスクロマトグラフィーに
よる分析では純度88.5％のNVAであり、蒸留収率は57.2
％であった。蒸留残渣は75.5gであり、粘度の高いター
ル状物質に変質していた。Comparative Example 1 Under the same conditions as in Example 1, 200 g of NVA (purity: 85.5%) was distilled without adding a stabilizer. Heating was continued for 3 hours, but the fraction was only 110.5 g. Analysis by gas chromatography showed NVA with a purity of 88.5% and a distillation yield of 57.2%.
%Met. The distillation residue weighed 75.5 g and had been transformed into a highly viscous tar-like substance.
実施例２ Ｎ−（α−ブトキシエチル）アセトアミドの熱分解に
より得られたNVA（純度52.5％）1560g及びジフェニルア
ミン0.5gを内容積500mlのナス型フラスコに入れ、浴温1
10℃、圧力4.5mmHgで減圧蒸留した。蒸留に要した時間
は約2.5時間であった。留出温度85.5℃〜89.5℃の留分7
77.8gが得られ、ガスクロマトグラフィーによる分析で
は純度99.5％のNVAであった。蒸留収率は94.5％であっ
た。Example 2 1560 g of NVA (purity: 52.5%) obtained by thermal decomposition of N- (α-butoxyethyl) acetamide and 0.5 g of diphenylamine were put into a 500 ml eggplant-shaped flask and the bath temperature was 1
Vacuum distillation was performed at 10 ° C. and a pressure of 4.5 mmHg. The time required for distillation was about 2.5 hours. Distillate 7 with a distillation temperature of 85.5 ° C to 89.5 ° C
77.8 g were obtained, and it was 99.5% NVA according to analysis by gas chromatography. The distillation yield was 94.5%.
実施例３〜11、比較例２〜４ 実施例２で用いた純度52.5％のNVAに種々の安定化剤
を加えて熱安定性を試験した。Examples 3 to 11, Comparative Examples 2 to 4 The thermal stability was tested by adding various stabilizers to the 52.5% pure NVA used in Example 2.
NVA10.0gに対して安定化剤を0.2重量％加え、110℃で
２時間加熱後、ガスクロマトグラフィーにより残存する
NVAを分析した。その結果及び比較例２として安定化剤
を加えない場合のNVAの残存率、また、比較例3,4として
一般のラジカル重合禁止剤を添加したときの結果を表１
に示した。0.2% by weight of a stabilizer is added to 10.0 g of NVA, heated at 110 ° C. for 2 hours, and left by gas chromatography.
NVA was analyzed. Table 1 shows the results and the residual ratio of NVA when no stabilizer was added as Comparative Example 2, and the results when a general radical polymerization inhibitor was added as Comparative Examples 3 and 4.
It was shown to.
実施例８ 実施例１で使用したものと同じNVA（純度85.5％）10
0.0g及び酢酸ナトリウム0.25gを試薬瓶に入れ密封し、1
50日間室温にて貯蔵した。ガスクロマトグラフィーによ
り分析したところNVAの2.3％が変質していた。 Example 8 Same NVA (purity 85.5%) as used in Example 1 10
Put 0.0g and 0.25g of sodium acetate in a reagent bottle and seal.
Stored at room temperature for 50 days. When analyzed by gas chromatography, 2.3% of the NVA was altered.
比較例５ 酢酸ナトリウムを添加しない以外は実施例８と同様に
NVAを室温で150日間貯蔵した。ガスクロマトグラフィー
により分析したところNVAの18.5％が変質していた。Comparative Example 5 Same as Example 8 except that sodium acetate was not added.
NVA was stored at room temperature for 150 days. When analyzed by gas chromatography, 18.5% of NVA was altered.
（６）発明の効果 本発明によれば、従来貯蔵時、蒸留精製時、または反
応時に変質し、損失を招く傾向のあったNVAに安定化剤
を添加することにより簡便かつ経済的に安定化を図るこ
とが可能である。(6) Effects of the Invention According to the present invention, the stabilizer is easily and economically stabilized by adding a stabilizer to NVA, which has been conventionally deteriorated during storage, distillation and purification, or during reaction, and which tends to cause loss. It is possible to achieve.
したがって、NVAの取り扱いに際して安定化剤を適宜
添加することによりNVAの一部が変質するのを防止で
き、そのためNVAの損失が避けられる。Therefore, it is possible to prevent a part of the NVA from being deteriorated by appropriately adding a stabilizer when handling the NVA, thereby avoiding the loss of the NVA.
Claims (1)
は弱酸のアンモニウム塩であって、該塩の水溶液がアル
カリ性を示す無機塩類、 炭素数１〜６の有機弱酸のアルカリ金属、アルカリ土
類金属塩またはアンモニウム塩、 から成る群から選択された少くとも１種の安定化剤を添
加することを特徴とするＮ−ビニルアセトアミドの安定
化方法。1. An N-vinylacetamide comprising an organic amine compound, a weak acid salt of an alkali metal or an alkaline earth metal or an ammonium salt of a weak acid, wherein the aqueous solution of the salt is an inorganic salt exhibiting alkalinity, having 1 to 6 carbon atoms. A method for stabilizing N-vinylacetamide, comprising adding at least one stabilizer selected from the group consisting of an alkali metal, alkaline earth metal salt or ammonium salt of an organic weak acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9418989A JP2619527B2 (en) | 1989-04-13 | 1989-04-13 | Method for stabilizing N-vinylacetamide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9418989A JP2619527B2 (en) | 1989-04-13 | 1989-04-13 | Method for stabilizing N-vinylacetamide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02270846A JPH02270846A (en) | 1990-11-05 |
| JP2619527B2 true JP2619527B2 (en) | 1997-06-11 |
Family
ID=14103359
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9418989A Expired - Fee Related JP2619527B2 (en) | 1989-04-13 | 1989-04-13 | Method for stabilizing N-vinylacetamide |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2619527B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2548051B2 (en) * | 1991-05-22 | 1996-10-30 | 日東化学工業株式会社 | Stabilization method of acrylamide aqueous solution |
| DE19519628B4 (en) * | 1994-05-30 | 2005-07-14 | Mitsubishi Chemical Corp. | Process for stabilizing N-vinylamides |
| JP2002167369A (en) * | 2000-09-19 | 2002-06-11 | Showa Denko Kk | Method for preparing high polymeric n-vinylcarboxylic acid amide |
-
1989
- 1989-04-13 JP JP9418989A patent/JP2619527B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH02270846A (en) | 1990-11-05 |
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