JP2005343845A - Polymerization inhibitor of acrylonitrile and method for inhibiting polymerization - Google Patents
Polymerization inhibitor of acrylonitrile and method for inhibiting polymerization Download PDFInfo
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本発明は、アクリロニトリルの製造時、精製時におけるアクリロニトリルの重合を抑制し、さらに重合によって生じる汚れの発生を効果的に抑制するアクリロニトリルの重合抑制剤および重合抑制方法に関するものである。 The present invention relates to an acrylonitrile polymerization inhibitor and a polymerization inhibition method that inhibits the polymerization of acrylonitrile during the production and purification of acrylonitrile, and further effectively suppresses the generation of dirt caused by the polymerization.
アクリロニトリルは、熱、光、その他の要因により極めて重合しやすく、製造、精製工程において、しばしば重合により関連設備内でファウリング（汚れ）が発生しトラブルを起こすことが知られている。汚れが、アクリロニトリルの製造工程、精製工程の製造タンク、蒸留塔（精留塔）、液送配管に付着すると、アクリロニトリルの製造・精製が制御できなくなり、操業に支障を来す。さらに製品品質の低下の原因ともなる。また、関連設備内に付着した重合反応物（汚れ）の除去は、人力による作業で行なわざるを得ないために、作業効率が悪く、その結果、長期間の運転停止を余儀なくされ、経済的損失が大きい。また、そこで、アクリロニトリル関連設備内での汚れを抑制する重合抑制剤および重合抑制方法が数多く提案・実施されてきた。 It is known that acrylonitrile is very easily polymerized due to heat, light, and other factors, and fouling (contamination) often occurs in related equipment during the production and purification processes, causing trouble. If dirt adheres to the acrylonitrile production process, the purification process production tank, the distillation tower (rectification tower), and the liquid feed pipe, the production and purification of acrylonitrile cannot be controlled, which hinders operations. In addition, it may cause a reduction in product quality. In addition, removal of the polymerization reaction product (dirt) adhering to the related equipment is unavoidable due to work by human power, resulting in poor work efficiency. As a result, it is necessary to stop the operation for a long time, resulting in economic loss. Is big. Accordingly, a number of polymerization inhibitors and polymerization suppression methods that suppress contamination in acrylonitrile-related facilities have been proposed and implemented.
一般に重合抑制剤としては、従来、ハイドロキノンやピロガロール（例えば、特許文献１参照）が用いられてきたが、十分な効果を示さず、これに替わる重合抑制剤としてヒドロキシアミン、フェニレンジアミン（例えば、特許文献２参照）、ニトロシルラジカル（例えば、特許文献３参照）の利用が提案されてきた。しかし、依然として十分な重合抑制効果を得るには至っていない。そのため、より優れたアクリロニトリルの重合抑制剤および効果的な重合抑制方法が強く望まれている。 In general, hydroquinone or pyrogallol (for example, see Patent Document 1) has been used as a polymerization inhibitor, but it does not show a sufficient effect, and hydroxyamine and phenylenediamine (for example, patents) as alternative polymerization inhibitors. The use of nitrosyl radicals (see, for example, Patent Document 3) has been proposed. However, a sufficient polymerization inhibitory effect has not yet been obtained. Therefore, a more excellent acrylonitrile polymerization inhibitor and an effective polymerization suppression method are strongly desired.
本発明は、アクリロニトリルの製造時、精製時におけるアクリロニトリルの重合を抑制し、さらに重合によって生じる汚れの発生を効果的に抑制するアクリロニトリルの重合抑制剤および重合抑制方法を提供することにある。 An object of the present invention is to provide an acrylonitrile polymerization inhibitor and a polymerization inhibition method that inhibits the polymerization of acrylonitrile during the production and purification of acrylonitrile, and further effectively suppresses the generation of dirt caused by the polymerization.
本発明者らは、アクリロニトリルの重合特性を詳細に検討した結果、特定のグリシン誘導体がアクリロニトリルの重合を極めて効率良く抑制することを見出し、本発明を成すにいたった。 As a result of examining the polymerization characteristics of acrylonitrile in detail, the present inventors have found that a specific glycine derivative suppresses the polymerization of acrylonitrile very efficiently, and have completed the present invention.
すなわち、請求項１に係る発明は、下記一般式（１）で表されるグリシン誘導体を有効成分として含むことを特徴とするアクリロニトリルの重合抑制剤である。 That is, the invention according to claim 1 is an acrylonitrile polymerization inhibitor comprising a glycine derivative represented by the following general formula (1) as an active ingredient.
請求項２に係る発明は、請求項１記載のアクリロニトリルの重合抑制剤であり、前記グリシン誘導体が、グリシン、Ｎ−メチルグリシン、Ｎ，Ｎ−ジメチルグリシン、Ｎ−アセチルグリシン、Ｎ、Ｎ−ジヒドロキシエチルグリシン、エチレン−Ｎ、Ｎ´−ジグリシン、エチレン−Ｎ、Ｎ´−ビスカルボキシメチル−Ｎ、Ｎ´−ジグリシン（エチレンジアミン四酢酸）、ニトリロトリ酢酸、ヒドロキシエチルイミノジ酢酸、ヒドロキシエチルエチレンジアミン三酢酸、ジエチレントリアミン五酢酸、トリエチレンテトラアミン六酢酸、Ｎ、Ｎ−ジカルボキシメチルグルタミン酸、１，３−プロパンジアミン四酢酸及び１，３−ジアミノ−２−ヒドロキシプロパン四酢酸から選ばれた少なくとも１種であることを特徴としている。 The invention according to claim 2 is the polymerization inhibitor of acrylonitrile according to claim 1, wherein the glycine derivative is glycine, N-methylglycine, N, N-dimethylglycine, N-acetylglycine, N, N-dihydroxy. Ethylglycine, ethylene-N, N′-diglycine, ethylene-N, N′-biscarboxymethyl-N, N′-diglycine (ethylenediaminetetraacetic acid), nitrilotriacetic acid, hydroxyethyliminodiacetic acid, hydroxyethylethylenediaminetriacetic acid, At least one selected from diethylenetriaminepentaacetic acid, triethylenetetraaminehexaacetic acid, N, N-dicarboxymethylglutamic acid, 1,3-propanediaminetetraacetic acid and 1,3-diamino-2-hydroxypropanetetraacetic acid It is characterized by that.
請求項３に係る発明は、アクリロニトリルの製造時、精製時において、前記一般式（１）で表されるグリシン誘導体をアクリロニトリルを含む工程液に添加することを特徴とするアクリロニトリルの重合抑制方法である。 The invention according to claim 3 is a method for inhibiting polymerization of acrylonitrile, wherein the glycine derivative represented by the general formula (1) is added to a process liquid containing acrylonitrile at the time of production and purification of acrylonitrile. .
請求項４に係る発明は、請求項３記載のアクリロニトリルの重合抑制方法であり、前記一般式（１）で表されるグリシン誘導体を工程中に含まれるアクリロニトリルに対して０．０５〜１０００ｐｐｍ添加することを特徴とする。 The invention according to claim 4 is the method for inhibiting polymerization of acrylonitrile according to claim 3, wherein the glycine derivative represented by the general formula (1) is added in an amount of 0.05 to 1000 ppm with respect to acrylonitrile contained in the process. It is characterized by that.
請求項５に係る発明は、請求項３又は４記載のアクリロニトリルの重合抑制方法であり、前記グリシン誘導体が、グリシン、Ｎ−メチルグリシン、Ｎ，Ｎ−ジメチルグリシン、Ｎ−アセチルグリシン、Ｎ、Ｎ−ジヒドロキシエチルグリシン、エチレン−Ｎ、Ｎ´−ジグリシン、エチレン−Ｎ、Ｎ´−ビスカルボキシメチル−Ｎ、Ｎ´−ジグリシン（エチレンジアミン四酢酸）、ニトリロトリ酢酸、ヒドロキシエチルイミノジ酢酸、ヒドロキシエチルエチレンジアミン三酢酸、ジエチレントリアミン五酢酸、トリエチレンテトラアミン六酢酸、Ｎ、Ｎ−ジカルボキシメチルグルタミン酸、１，３−プロパンジアミン四酢酸及び１，３−ジアミノ−２−ヒドロキシプロパン四酢酸から選ばれた少なくとも１種であることを特徴とする。 The invention according to claim 5 is the method for inhibiting polymerization of acrylonitrile according to claim 3 or 4, wherein the glycine derivative is glycine, N-methylglycine, N, N-dimethylglycine, N-acetylglycine, N, N -Dihydroxyethylglycine, ethylene-N, N'-diglycine, ethylene-N, N'-biscarboxymethyl-N, N'-diglycine (ethylenediaminetetraacetic acid), nitrilotriacetic acid, hydroxyethyliminodiacetic acid, hydroxyethylethylenediamine At least one selected from acetic acid, diethylenetriaminepentaacetic acid, triethylenetetraaminehexaacetic acid, N, N-dicarboxymethylglutamic acid, 1,3-propanediaminetetraacetic acid and 1,3-diamino-2-hydroxypropanetetraacetic acid It is characterized by being.
本発明のアクリロニトリルの重合抑制剤およびアクリロニトリルの重合抑制方法により、アクリロニトリルの製造、精製時における重合を効果的に抑制することができ、特にアクリロニトリル製造・精製時の操業の安定化、アクリロニトリルの品質の向上に大きく寄与することができる。 By the polymerization inhibitor of acrylonitrile and the method of inhibiting polymerization of acrylonitrile of the present invention, it is possible to effectively suppress polymerization during the production and purification of acrylonitrile, especially the stabilization of the operation during the production and purification of acrylonitrile, the quality of acrylonitrile. This can greatly contribute to improvement.
本発明は、アクリロニトリルの製造時、精製時において、特定のグリシン誘導体を含むアクリロニトリル重合抑制剤および該アクリロニトリル重合抑制剤を用いることによって、アクリロニトリルの重合によって生じる汚れの発生抑制を効果的に達成し得るアクリロニトリル重合抑制方法である。 INDUSTRIAL APPLICABILITY In the production and purification of acrylonitrile, by using an acrylonitrile polymerization inhibitor containing a specific glycine derivative and the acrylonitrile polymerization inhibitor, the present invention can effectively achieve the suppression of occurrence of dirt caused by the polymerization of acrylonitrile. This is a method for inhibiting acrylonitrile polymerization.
本発明において重合抑制の対象となるアクリロニトリルは、特に限定されるものではなく、通常のアクリロニトリルの製造方法により得られるアクリロニトリルであり、具体的には次の方法により得られるアクリロニトリルである。（１）プロピレンをアンモ酸化してアクリロニトリルを製造する方法（例えばソハイオ法、ＳＮＡＭ法）、（２）エチレンクロロヒドリンにシアン化ナトリウムを作用させ、エチレンシアンヒドリンとして脱水してアクリロニトリルを得る方法、（３）エチレンオキサイドを原料としてシアン化水素をアルカリ性触媒下で液相反応させてエチレンシアンヒドリンとし、これを脱水してアクリロニトリルを得る方法、（４）アセトアルデヒドとシアン化水素を触媒の存在下で反応させラクトニトリルを得、これを脱水してアクリロニトリルを製造する方法（ラクトニトリル法）等があげられる。 In the present invention, the acrylonitrile to be subjected to polymerization inhibition is not particularly limited, and is acrylonitrile obtained by an ordinary method for producing acrylonitrile, specifically, acrylonitrile obtained by the following method. (1) A method for producing acrylonitrile by ammoxidation of propylene (for example, Sohio method, SNA method), (2) A method in which sodium cyanohydride is allowed to act on ethylene chlorohydrin and dehydrated as ethylene cyanohydrin to obtain acrylonitrile (3) A method in which ethylene oxide is used as a raw material and hydrogen cyanide is subjected to a liquid phase reaction in the presence of an alkaline catalyst to obtain ethylene cyanohydrin, which is dehydrated to obtain acrylonitrile. (4) Acetaldehyde and hydrogen cyanide are reacted in the presence of a catalyst. Examples thereof include a method for obtaining lactonitrile and dehydrating it to produce acrylonitrile (lactonitrile method).
本発明におけるグリシン誘導体は、一般式（１）で表される化合物であり、式中、Ｒ１、Ｒ２はそれぞれ独立に水素原子、アセチル基、アミノアセチル基、Ｎ−（アミノアセチル）アミノアセチル基、フェニルアセチル基、カルバモイル基、ベンゾイル基、フタロイル基、ヒドロキシル基を含んでいてもよい炭素数１〜８のアルキル基、ヒドロキシル基を含んでいてもよい炭素数６〜１９のアリール基もしくはアルキルフェニル基、１〜３個のカルボキシル基を含んでいてもよい炭素数２〜６のカルボキシアルキル基、１〜２個のカルボキシメチル基及び／又はヒドロキシエチル基を含む炭素数４〜７のアミノアルキル基、１〜３個のカルボキシメチル基及び／又はヒドロキシエチル基を含むアルキレン（炭素数２〜３）ジアミノアルキル（炭素数２〜３）基、１〜４個のカルボキシメチル基及び／又はヒドロキシエチル基を含むジアルキレン（炭素数２〜３）トリアミノアルキル（炭素数２〜３）基、及び／又はその完全中和塩あるいは部分中和塩であり、Ｘは水素原子、ナトリウム、カリウムである。 The glycine derivative in the present invention is a compound represented by the general formula (1), in which R 1 and R 2 are each independently a hydrogen atom, an acetyl group, an aminoacetyl group, or N- (aminoacetyl) aminoacetyl. Group, phenylacetyl group, carbamoyl group, benzoyl group, phthaloyl group, alkyl group having 1 to 8 carbon atoms which may contain hydroxyl group, aryl group or alkyl having 6 to 19 carbon atoms which may contain hydroxyl group A phenyl group, a carboxyalkyl group having 2 to 6 carbon atoms which may contain 1 to 3 carboxyl groups, an aminoalkyl having 4 to 7 carbon atoms containing 1 to 2 carboxymethyl groups and / or a hydroxyethyl group; Group, alkylene containing 1 to 3 carboxymethyl groups and / or hydroxyethyl groups (2 to 3 carbon atoms) diaminoalkyl Dialkylene (2 to 3 carbon atoms) triaminoalkyl (2 to 3 carbon atoms) group containing 2 to 3 carbon groups, 1 to 4 carboxymethyl groups and / or hydroxyethyl groups, and / or its complete X is a hydrogen atom, sodium, or potassium.
具体的には、グリシン、Ｎ−メチルグリシン、Ｎ−エチルグリシン、Ｎ−プロピルグリシン、Ｎ−ヒドロキシメチルグリシン、Ｎ−カルボキシメチルグリシン、Ｎ−フェニルグリシン、Ｎ−ベンジルグリシン、Ｎ−アセチルグリシン、Ｎ−フェニルアセチルグリシン、Ｎ−カルバモイルグリシン、Ｎ−ベンゾイルグリシン、Ｎ−トルイルグリシン、Ｎ−トリフェニルメチルグリシン、Ｎ−（４−ヒドロキシフェニル）グリシン、Ｎ−フタロイルグリシン、Ｎ−（グリシルグリシン、グリシルグリシルグリシン、Ｎ，Ｎ−ジメチルグリシン、Ｎ，Ｎ−ジエチルグリシン、Ｎ，Ｎ−ジプロピルグリシン、Ｎ，Ｎ−ジヒドロキシエチルグリシン、Ｎ，Ｎ−ジ（２−ヒドロキシエチル）グリシン、Ｎ−ジヒドロキシブチルグリシン、ヒドロキシエチルイミノジ酢酸、エチレン−Ｎ、Ｎ’−ジグリシン、ニトリロ三酢酸、ジカルボキシメチルグルタミン酸、Ｎ−（２−ヒドロキシエチル）エチレンジアミン三酢酸、エチレンジアミン四酢酸、１，３−プロパンジアミン四酢酸、１，３−ジアミノ−２−ヒドロキシプロパン四酢酸、ジエチレントリアミン五酢酸、トリエチレンテトラアミン六酢酸等がある。好ましくは、グリシン、Ｎ−メチルグリシン、Ｎ，Ｎ−ジメチルグリシン、Ｎ，Ｎ−ジヒドロキシエチルグリシン、ジヒドロキシブチルグリシン、Ｎ−アセチルグリシン、ヒドロキシエチルイミノジ酢酸、エチレン−Ｎ、Ｎ’−ジグリシン、ニトリロ三酢酸、Ｎ，Ｎ−ジカルボキシメチルグルタミン酸、Ｎ−カルボキシメチル−Ｎ‘−（２−ヒドロキシエチル）−Ｎ，Ｎ’−エチレングリシン、エチレンジアミン四酢酸、１，３−プロパンジアミン四酢酸、１，３−ジアミノ−２−ヒドロキシプロパン四酢酸、ジエチレントリアミン五酢酸、トリエチレンテトラアミン六酢酸である。これらのグリシン誘導体の単独あるいは２種類以上を組み合わせて用いても良い。 Specifically, glycine, N-methyl glycine, N-ethyl glycine, N-propyl glycine, N-hydroxymethyl glycine, N-carboxymethyl glycine, N-phenyl glycine, N-benzyl glycine, N-acetyl glycine, N -Phenylacetylglycine, N-carbamoylglycine, N-benzoylglycine, N-toluylglycine, N-triphenylmethylglycine, N- (4-hydroxyphenyl) glycine, N-phthaloylglycine, N- (glycylglycine, Glycylglycylglycine, N, N-dimethylglycine, N, N-diethylglycine, N, N-dipropylglycine, N, N-dihydroxyethylglycine, N, N-di (2-hydroxyethyl) glycine, N- Dihydroxybutyl glycine, hydroxyethyl Minodiacetic acid, ethylene-N, N′-diglycine, nitrilotriacetic acid, dicarboxymethylglutamic acid, N- (2-hydroxyethyl) ethylenediaminetriacetic acid, ethylenediaminetetraacetic acid, 1,3-propanediaminetetraacetic acid, 1,3- Diamino-2-hydroxypropanetetraacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraaminehexaacetic acid, etc. Preferably, glycine, N-methylglycine, N, N-dimethylglycine, N, N-dihydroxyethylglycine, dihydroxybutyl Glycine, N-acetylglycine, hydroxyethyliminodiacetic acid, ethylene-N, N′-diglycine, nitrilotriacetic acid, N, N-dicarboxymethylglutamic acid, N-carboxymethyl-N ′-(2-hydroxyethyl)- N, N'-ethylene grease Ethylenediaminetetraacetic acid, 1,3-propanediaminetetraacetic acid, 1,3-diamino-2-hydroxypropanetetraacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraaminehexaacetic acid, alone or in combination of these two glycine derivatives. A combination of the above may also be used.
本発明のアクリロニトリルの重合抑制剤は、常温で液体、固体の形態のグリシン誘導体を１〜１００重量％として含むものである。具体的には、グリシン誘導体をそのまま単独で用いる外に、グリシン誘導体を溶剤に溶解して成るものである。用いる溶剤は、適用するアクリロニトリルの工程と用いるグリシン誘導体を考慮して、適宜選択決定されれば良く、通常、水、エチレングリコール、エタノール等が挙げられ、これらの中でも水が最も好ましい。グリシン誘導体の配合量が、１重量％未満では本発明の効果を十分に発揮することができない場合がある。 The polymerization inhibitor of acrylonitrile of the present invention contains 1 to 100% by weight of a glycine derivative in a liquid or solid form at room temperature. Specifically, in addition to using the glycine derivative alone as it is, the glycine derivative is dissolved in a solvent. The solvent to be used may be appropriately selected and determined in consideration of the acrylonitrile process to be applied and the glycine derivative to be used. Usually, water, ethylene glycol, ethanol and the like are mentioned, and among these, water is most preferable. If the blending amount of the glycine derivative is less than 1% by weight, the effects of the present invention may not be sufficiently exerted.
本発明のアクリロニトリル重合抑制剤の製造は、特に限定されるものではなく、撹拌下、溶剤にグリシン誘導体を添加して均一溶液として調製して得られる。 The production of the acrylonitrile polymerization inhibitor of the present invention is not particularly limited, and can be obtained by adding a glycine derivative to a solvent under stirring and preparing it as a uniform solution.
また、本発明のグリシン誘導体に従来より使用されている、その他の重合禁止剤を本発明の効果を妨げない範囲で配合することができる。 Moreover, the other polymerization inhibitor conventionally used for the glycine derivative of this invention can be mix | blended in the range which does not prevent the effect of this invention.
本発明のアクリロニトリル重合抑制方法は、一般式（１）で表されたグリシン誘導体を含むアクリロニトリル重合抑制剤をアクリロニトリルの製造時、精製時において、アクリロニトリルおよびアクリロニトリルを含む工程液に添加することによって、アクリロニトリルの重合抑制および重合によって生じる汚れの発生抑制を効果的に達成し得るアクリロニトリル重合抑制方法である。 According to the method for inhibiting acrylonitrile polymerization of the present invention, an acrylonitrile polymerization inhibitor containing a glycine derivative represented by the general formula (1) is added to a process liquid containing acrylonitrile and acrylonitrile at the time of production and purification of acrylonitrile. This is a method for inhibiting the polymerization of acrylonitrile, which can effectively achieve the inhibition of polymerization and the occurrence of contamination caused by polymerization.
本発明のアクリロニトリル重合抑制方法を実施するに際して、重合抑制剤の添加箇所は、アクリロニトリルの製造工程内においては、アクリロニトリルを含む工程液の一部が重合し、その重合物が付着し汚れとなる箇所の手前であり、具体的にはプロピレンをアンモ酸化してアクリロニトリルを製造するソハイオ法、ＳＮＡＭ法、エチレンシアンヒドリンとして脱水してアクリロニトリルを得る方法、エチレンシアンヒドリンを脱水してアクリロニトリルを得る方法、ラクトニトリルを脱水してアクリロニトリルを製造するラクトニトリル法等の脱水塔あるいはそのフィード液、アクリロニトリル精製塔あるいはそのフィード液、およびその周辺の工程に添加される。また、貯蔵時や輸送時には保管タンク、貯蔵タンク、移送タンク等の貯蔵設備に添加される。 When carrying out the acrylonitrile polymerization inhibition method of the present invention, the polymerization inhibitor is added at a location where, in the acrylonitrile production process, a part of the process liquid containing acrylonitrile is polymerized and the polymer adheres and becomes soiled. Specifically, the Sohio method for producing acrylonitrile by ammoxidizing propylene, the SNA method, the method for obtaining acrylonitrile by dehydrating as ethylene cyanohydrin, the method for obtaining acrylonitrile by dehydrating ethylene cyanohydrin In addition, it is added to a dehydration tower such as a lactonitrile method for producing acrylonitrile by dehydrating lactonitrile or a feed liquid thereof, an acrylonitrile purification tower or a feed liquid thereof, and the surrounding steps. In addition, it is added to storage facilities such as storage tanks, storage tanks, and transfer tanks during storage and transportation.
本発明の重合抑制剤の添加量は、適用するアクリロニトリルの工程と必要とする重合抑制の程度を考慮して決定され、通常はグリシン誘導体として工程液中に含まれるアクリロニトリルに対して０．０５〜１０００ｐｐｍ、好ましくは、０．５〜１００ｐｐｍである。グリシン誘導体を１０００ｐｐｍより多く用いることは、なんら妨げるものではないが、添加量に見合った効果の向上がみられず、経済的な見地から不利なことがある。 The addition amount of the polymerization inhibitor of the present invention is determined in consideration of the acrylonitrile process to be applied and the degree of polymerization inhibition required, and is usually 0.05 to acrylonitrile contained in the process liquid as a glycine derivative. 1000 ppm, preferably 0.5 to 100 ppm. Use of more than 1000 ppm of glycine derivative is not hindered at all, but the effect corresponding to the amount added is not improved, which may be disadvantageous from an economic standpoint.
本発明のアクリロニトリル重合抑制剤の添加方法は、特に限定されるものではなく、通常の薬液注入ポンプを用いて添加される。 The addition method of the acrylonitrile polymerization inhibitor of this invention is not specifically limited, It adds using a normal chemical solution injection pump.
本発明を実施例により更に詳しく説明するが、本発明はこれらの実施例に限定されるものではない。 Examples The present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
（グリシン誘導体）
Ｇ−１：グリシン
Ｇ−２：Ｎ−メチルグリシン
Ｇ−３：Ｎ，Ｎ−ジメチルグリシン
Ｇ−４：Ｎ−アセチルグリシン
Ｇ−５：Ｎ，Ｎ−ジヒドロキシエチルグリシン
Ｇ−６：エチレン−Ｎ，Ｎ’−ジグリシン
Ｇ−７：エチレン−Ｎ，Ｎ’−ビスカルボキシメチル−Ｎ，Ｎ’−ジグリシン（エチレンジアミン四酢酸）
Ｇ−８：ニトリロトリ酢酸
Ｇ−９：ヒドロキシエチルイミノジ酢酸
Ｇ−１０：ヒドロキシエチルエチレンジアミン三酢酸
Ｇ−１１：ジエチレントリアミン五酢酸
Ｇ−１２：トリエチレンテトラアミン六酢酸
Ｇ−１３：Ｎ，Ｎ−ジカルボキシメチルグルタミン酸
Ｇ−１４：１，３−プロパンジアミン四酢酸
Ｇ−１５：１，３−ジアミノ−２−ヒドロキシプロパン四酢酸
(Glycine derivative)
G-1: Glycine G-2: N-methylglycine G-3: N, N-dimethylglycine G-4: N-acetylglycine G-5: N, N-dihydroxyethylglycine G-6: ethylene-N, N′-diglycine G-7: ethylene-N, N′-biscarboxymethyl-N, N′-diglycine (ethylenediaminetetraacetic acid)
G-8: Nitrilotriacetic acid G-9: Hydroxyethyliminodiacetic acid G-10: Hydroxyethylethylenediaminetriacetic acid G-11: Diethylenetriaminepentaacetic acid G-12: Triethylenetetraaminehexaacetic acid G-13: N, N-di Carboxymethylglutamic acid G-14: 1,3-propanediaminetetraacetic acid G-15: 1,3-diamino-2-hydroxypropanetetraacetic acid
（比較例）
ＨＱ：ハイドロキノン
ＭＱ：ハイドロキノンモノメチルエーテル
ＰＴＺ：フェノチアジン
ＤＥＨＡ：Ｎ，Ｎ−ジエチルヒドロキシルアミン
ＰＤＡ：Ｎ，Ｎ’−ジ−第二−ブチル−ｐ−フェニレンジアミン
(Comparative example)
HQ: hydroquinone MQ: hydroquinone monomethyl ether PTZ: phenothiazine DEHA: N, N-diethylhydroxylamine PDA: N, N′-di-secondary-butyl-p-phenylenediamine
重合抑制試験１
５００ｍＬ三口フラスコにアクリロニトリル２００ｇと所定量のグリシン誘導体を添加し、窒素ガスを５０ｍＬ／分の割合で導入しながら、７８℃（常圧）にて８時間、加熱還流した。８時間後、反応液約５ｇを採取し、正確に秤量した後、１μｍガラス繊維瀘紙〔ミリポア社（Ｍｉｌｌｉｐｏｒｅ Ｃｏｒｐ．）製〕にて瀘別し、生成したポリマーを分離した。分離したポリマーを５０℃で６時間乾燥した後、秤量し、反応液中の生成ポリマー量（重量ｐｐｍ）を算出した。結果を表１に示した。
Polymerization inhibition test 1
200 g of acrylonitrile and a predetermined amount of glycine derivative were added to a 500 mL three-necked flask, and the mixture was heated to reflux at 78 ° C. (normal pressure) for 8 hours while introducing nitrogen gas at a rate of 50 mL / min. After 8 hours, about 5 g of the reaction solution was collected and weighed accurately, and then separated with 1 μm glass fiber paper (Millipore Corp.) to separate the produced polymer. The separated polymer was dried at 50 ° C. for 6 hours and then weighed to calculate the amount of polymer produced (weight ppm) in the reaction solution. The results are shown in Table 1.
本発明の重合抑制剤は、従来のアクリロニトリル重合抑制剤であるハイドロキノン（ＨＱ）、ハイドロキノンモノメチルエーテル（ＭＱ）、フェノチアジン（ＰＴＺ）、Ｎ，Ｎ−ジエチルヒドロキシルアミン（ＤＥＨＡ）、Ｎ，Ｎ’−ジ−第二−ブチル−ｐ−フェニレンジアミン（ＰＤＡ）のいずれと比較しても同一添加量では、圧倒的に少ないポリマー生成量であり、優れた重合防止効果を発揮していることが分かる。 The polymerization inhibitor of the present invention includes hydroquinone (HQ), hydroquinone monomethyl ether (MQ), phenothiazine (PTZ), N, N-diethylhydroxylamine (DEHA), N, N′-di, which are conventional acrylonitrile polymerization inhibitors. -Comparing to any of -secondary-butyl-p-phenylenediamine (PDA), it can be seen that with the same addition amount, the amount of polymer production is overwhelmingly small and an excellent polymerization preventing effect is exhibited.
Claims (5)
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