JP2006069916A - Polymerization inhibitor for vinyl acetate and polymerization-inhibiting method - Google Patents
Polymerization inhibitor for vinyl acetate and polymerization-inhibiting method Download PDFInfo
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本発明は、酢酸ビニルの製造工程、精製工程、貯蔵および輸送工程における酢酸ビニ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 a polymerization inhibitor and a polymerization inhibition method for vinyl acetate in vinyl acetate production, purification, storage, and transportation.
酢酸ビニルは、極めて重合しやすく、製造工程、精製工程、反応工程において、熱、光、その他の要因により、しばしば重合トラブルを起こすことが知られている。このような重合は酢酸ビニルの製造工程、精製工程での汚れ（ファウリング）の原因となっている。このような汚れが、酢酸ビニルの製造工程、精製工程の製造タンク、蒸留塔（精留塔塔）、液送配管に付着すると、酢酸ビニルの製造・精製が制御できなくなり、操業に支障を来す場合がある。さらに製品品質の低下の原因ともなる。また、酢酸ビニルの汚れ、およびその重合反応物の除去は、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引き起こし、経済的損失が大きい。そこで、種々の酢酸ビニルの汚れ抑制剤、汚れ抑制方法や重合抑制剤、重合抑制方法が提案・実施されてきた。 It is known that vinyl acetate is very easily polymerized, and often causes polymerization troubles due to heat, light, and other factors in the production process, purification process, and reaction process. Such polymerization is a cause of fouling in the production process and the purification process of vinyl acetate. If such dirt adheres to the vinyl acetate production process, the purification process production tank, the distillation tower (rectification tower), or the liquid feed piping, the production and purification of vinyl acetate becomes uncontrollable, which hinders operations. There is a case. In addition, it may cause a reduction in product quality. Further, the removal of the vinyl acetate stains and the polymerization reaction product must be carried out by manual work, so that the work efficiency is poor. As a result, the operation is stopped for a long time, resulting in a large economic loss. Accordingly, various vinyl acetate stain inhibitors, stain inhibition methods, polymerization inhibitors, and polymerization inhibition methods have been proposed and implemented.
例えば、ハイドロキノン、ベンゾキノン、ｔ−ブチルカテコールを使用する方法（例えば特許文献１参照）、酢酸ビニルの蒸留工程の蒸留段階を通してｐ−アルキルフェノールを溶解状態で維持させて蒸留を行なう方法（例えば特許文献１、特許文献２参照）、ニトロキシルラジカル類を用いる方法（例えば特許文献３、特許文献４参照）等が開示されている。 For example, a method using hydroquinone, benzoquinone and t-butylcatechol (see, for example, Patent Document 1), a method in which p-alkylphenol is maintained in a dissolved state throughout the distillation step of vinyl acetate (for example, Patent Document 1). And Patent Document 2), methods using nitroxyl radicals (see, for example, Patent Document 3 and Patent Document 4), and the like are disclosed.
本発明は、酢酸ビニルの製造工程、精製工程、貯蔵および輸送工程における酢酸ビニルの重合を抑制し、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酢酸ビニ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。 The present invention relates to a polymerization inhibitor and a polymerization inhibition method for vinyl acetate that inhibits the polymerization of vinyl acetate in the production process, purification process, storage and transport process of vinyl acetate, and further effectively suppresses the occurrence of dirt caused by the polymerization. It is to provide.
本発明者らは、酢酸ビニルの重合特性を詳細に検討した結果、特定の有機酸が酢酸ビニ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 vinyl acetate in detail, the present inventors have found that a specific organic acid suppresses the polymerization of vinyl acetate very efficiently, and have come to achieve the present invention.
即ち、請求項１に係る発明は、酢酸ビニルの製造工程、精製工程、貯蔵および輸送工程において、一般式（１）（式中、Ｘ、Ｙはそれぞれ独立に水素原子、ヒドロキシル基あるいはカルボキシル基を有してもよい炭素数１から８のアルキル基を示す。）で表されるα−ヒドロキシカルボン酸およびアスコルビン酸からなる有機酸および／又はその水溶性塩から選ばれた１種以上を有効成分として含むことを特徴とする酢酸ビニルの重合抑制剤である。 That is, in the invention according to claim 1, in the vinyl acetate production process, purification process, storage and transport process, the general formula (1) (wherein X and Y are each independently a hydrogen atom, a hydroxyl group or a carboxyl group). An alkyl group having 1 to 8 carbon atoms which may have an active ingredient) selected from the group consisting of an organic acid composed of α-hydroxycarboxylic acid and ascorbic acid and / or a water-soluble salt thereof. It is a polymerization inhibitor of vinyl acetate characterized by including as above.
請求項３に係る発明は、酢酸ビニルの製造工程、精製工程、貯蔵および輸送工程において、酢酸ビニルを含む工程液に前記一般式（１）（式中、Ｘ、Ｙはそれぞれ独立に水素原子、ヒドロキシル基あるいはカルボキシル基を有してもよい炭素数１から８のアルキル基を示す。）で表されるα−ヒドロキシカルボン酸およびアスコルビン酸からなる有機酸および／又はその水溶性塩から選ばれた１種以上を添加することを特徴とする酢酸ビニルの重合抑制方法である。 According to a third aspect of the present invention, in the vinyl acetate production process, purification process, storage and transport process, the process liquid containing vinyl acetate contains the general formula (1) (wherein X and Y are each independently a hydrogen atom, An alkyl group having 1 to 8 carbon atoms which may have a hydroxyl group or a carboxyl group.) Selected from organic acids consisting of α-hydroxycarboxylic acid and ascorbic acid and / or water-soluble salts thereof. It is a method of inhibiting polymerization of vinyl acetate, characterized by adding one or more kinds.
請求項４に係る発明は、請求項３記載の酢酸ビニル重合抑制方法であり、有機酸および／又はその水溶性塩を工程液中の酢酸ビニルに対して０．０５〜１０００ｐｐｍ添加することを特徴とする。 The invention according to claim 4 is the vinyl acetate polymerization inhibiting method according to claim 3, characterized in that 0.05 to 1000 ppm of an organic acid and / or a water-soluble salt thereof is added to vinyl acetate in the process liquid. And
本発明の酢酸ビニルの重合抑制剤および酢酸ビニルの重合抑制方法により、酢酸ビニルの製造工程、精製工程、貯蔵工程および輸送工程における酢酸ビニルの重合を効果的に抑制し、さらに酢酸ビニルの重合により生じる酢酸ビニルを含む工程液に接する箇所の汚れの付着を防止する。その結果、酢酸ビニル製造時の操業の安定化、酢酸ビニルの品質の向上に大きく寄与することができる。 The vinyl acetate polymerization inhibitor and the vinyl acetate polymerization suppression method of the present invention effectively inhibits vinyl acetate polymerization in the vinyl acetate production process, purification process, storage process and transport process, and further by vinyl acetate polymerization. Prevents the adhesion of stains at locations in contact with the process liquid containing vinyl acetate. As a result, it can greatly contribute to the stabilization of operations during the production of vinyl acetate and the improvement of the quality of vinyl acetate.
本発明は、酢酸ビニルの製造工程、精製工程、貯蔵および輸送工程において、特定の有機酸および／又はその水溶性塩を有効成分として含む酢酸ビニルの重合抑制剤、および特定の有機酸および／又はその水溶性塩を用いることによって、酢酸ビニ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酢酸ビニルの重合抑制方法である。 The present invention relates to a vinyl acetate polymerization inhibitor containing a specific organic acid and / or a water-soluble salt thereof as an active ingredient in a vinyl acetate production process, purification process, storage and transport process, and a specific organic acid and / or By using the water-soluble salt, this is a method for inhibiting the polymerization of vinyl acetate, which can effectively achieve the inhibition of polymerization of vinyl acetate and the suppression of the occurrence of dirt caused by the polymerization.
本発明において対象となる工程は、酢酸ビニル化合物の製造工程、酢酸ビニル製造後の酢酸ビニルの精製工程、製造および精製した酢酸ビニルを貯蔵・保管する貯蔵工程、および製造、精製および貯蔵・保管した酢酸ビニルを移送・輸送する輸送工程であり、さらに各工程で酢酸ビニルを含む工程液と接する周辺設備・機器を含む循環系や回収系も包含する。具体的には、製造工程における酢酸ビニルの合成反応塔および反応後の反応物排出ラインや回収循環ライン、精製工程における精製塔への酢酸ビニルのフィード配管や予熱ラインおよび冷却ラインさらに循環ライン、貯蔵工程における保管タンクや貯蔵タンク、輸送工程における移送タンクおよび輸送タンクさらにその移送ラインなどがある。 The target process in the present invention includes a production process of a vinyl acetate compound, a purification process of vinyl acetate after the production of vinyl acetate, a storage process for storing and storing the produced and purified vinyl acetate, and a production, purification, storage and storage. It is a transport process for transporting and transporting vinyl acetate, and further includes a circulation system and a recovery system including peripheral equipment and devices that come into contact with a process liquid containing vinyl acetate in each process. Specifically, vinyl acetate synthesis reaction tower in the production process, reaction product discharge line and recovery circulation line after the reaction, vinyl acetate feed piping, preheating line and cooling line to the purification tower in the purification process, circulation line, storage There are storage tanks and storage tanks in the process, transfer tanks and transport tanks in the transport process, and their transfer lines.
本発明において対象となる酢酸ビニルは、特に限定されるものではなく、通常の酢酸ビニルの製造方法により得られる酢酸ビニルである。具体的には、触媒の存在下、反応塔にエチレンガス、酢酸、酸素ガス（分子状酸素）を導入して反応させて粗酢酸ビニルを得、蒸留によって精製して得られる酢酸ビニルである。代表的な製造方法としては、Pd系触媒を用いるエチレンのＩＣＩ法（液相）、Ｂａｙｅｒ法（気相）、Ｎａｔｉｏｎａｌ Ｄｉｓｔｉｌｌｅｒｓ（原Ｍｉｌｌｅｎｎｉｕｍ）法があり、いずれの方法で製造された酢酸ビニルにも適用することができる。 The vinyl acetate used in the present invention is not particularly limited, and is vinyl acetate obtained by a normal method for producing vinyl acetate. Specifically, it is vinyl acetate obtained by introducing ethylene gas, acetic acid, and oxygen gas (molecular oxygen) into a reaction tower in the presence of a catalyst to cause reaction to obtain crude vinyl acetate and purifying it by distillation. Typical production methods include the ICI method (liquid phase), the Bayer method (gas phase), and the National Distillers (original Millennium) method of ethylene using a Pd-based catalyst. Can be applied.
本発明で用いる有機酸および／又はその水溶性塩（以下、「本発明の有機酸類」とする。）は、α−ヒドロキシカルボン酸、アスコルビン酸およびその水溶性塩である。α−ヒドロキシカルボン酸は一般式（１）で表される天然系及び合成系のα−ヒドロキシカルボン酸であり、式中X、Yは独立して水素原子あるいは炭素数１から８のヒドロキシル基あるいはカルボキシル基を有してもよいアルキル基である。具体的なα−ヒドロキシカルボン酸としては、２−ヒドロキシ−4−メチルペンタン酸、２−ヒドロキシブタン酸、２−ヒドロキシヘキサン酸、２−ヒドロキシ−３，３−ジメチルブタン酸、２−ヒドロキシ−２−メチルプロパン酸、２−ヒドロキシ−３−メチルブタン酸、マンデル酸、２−ヒドロキシ−４−メトキシマンデル酸、４−ヒドロキシ−３−メトキシマンデル酸、２−ヒドロキシ−２−メチルブタン酸、グリセリン酸、グリコール酸、乳酸、酒石酸、クエン酸、リンゴ酸、グルコン酸、ヘプトン酸等であり、好ましくはグリコール酸、乳酸、酒石酸、クエン酸、リンゴ酸、グルコン酸、ヘプトン酸、より好ましくはクエン酸、グルコン酸である。これらのα−ヒドロキシカルボン酸の多くはヒドロキシル基が置換している炭素がキラル中心であるために光学活性であり、本発明においては何れか一方の異性体のみを使用しても、両者の等量混合物であるラセミ体を使用してもよい。通常は、経済的な見地から安価な異性体が選ばれる。 The organic acid and / or water-soluble salt thereof (hereinafter referred to as “organic acid of the present invention”) used in the present invention is α-hydroxycarboxylic acid, ascorbic acid and water-soluble salt thereof. The α-hydroxycarboxylic acid is a natural or synthetic α-hydroxycarboxylic acid represented by the general formula (1), wherein X and Y are independently a hydrogen atom, a hydroxyl group having 1 to 8 carbon atoms, or An alkyl group which may have a carboxyl group. Specific examples of α-hydroxycarboxylic acid include 2-hydroxy-4-methylpentanoic acid, 2-hydroxybutanoic acid, 2-hydroxyhexanoic acid, 2-hydroxy-3,3-dimethylbutanoic acid, and 2-hydroxy-2. -Methylpropanoic acid, 2-hydroxy-3-methylbutanoic acid, mandelic acid, 2-hydroxy-4-methoxymandelic acid, 4-hydroxy-3-methoxymandelic acid, 2-hydroxy-2-methylbutanoic acid, glyceric acid, glycol Acid, lactic acid, tartaric acid, citric acid, malic acid, gluconic acid, heptonic acid, etc., preferably glycolic acid, lactic acid, tartaric acid, citric acid, malic acid, gluconic acid, heptonic acid, more preferably citric acid, gluconic acid It is. Many of these α-hydroxycarboxylic acids are optically active because the carbon substituted with a hydroxyl group is a chiral center. In the present invention, even if only one of the isomers is used, Racemic mixtures that are quantitative mixtures may be used. Usually, cheap isomers are selected from an economic point of view.
また、本発明で用いるアスコルビン酸は、特に限定されるものではなく、天然系および合成系のアスコルビン酸が使用できる。さらにアスコルビン酸の光学異性体であるエリソルビン酸、イソアスコルビン酸等も用いることができる。 Further, the ascorbic acid used in the present invention is not particularly limited, and natural and synthetic ascorbic acid can be used. Furthermore, erythorbic acid, isoascorbic acid and the like, which are optical isomers of ascorbic acid, can also be used.
本発明の有機酸の水溶性塩としては、完全中和あるいは部分中和のナトリウム塩、カリウム塩およびこれらの複合塩である。 The water-soluble salt of the organic acid of the present invention is a completely neutralized or partially neutralized sodium salt, potassium salt or a complex salt thereof.
本発明において、これらの有機酸および／又はその水溶性塩を単独あるいは２種以上を組み合わせて用いても良い。 In the present invention, these organic acids and / or water-soluble salts thereof may be used alone or in combination of two or more.
本発明の酢酸ビニルの重合抑制剤としては、本発明の有機酸類の単独あるいは２種以上をそのまま用いた重合抑制剤と、本発明の有機酸類の単独あるいは２種以上を溶剤に溶解して用いる重合抑制剤があり、いずれでも良い。本発明の有機酸類を溶剤に溶解した重合抑制剤における有機酸類の濃度は、一律に決められるものではなく、対象とする工程や用いた有機酸およびその水溶性塩を考慮して適宜決定されれば良いが、一般には１〜５０重量％濃度である。また、用いる溶剤は、対象とする工程や用いた有機酸およびその水溶性塩を考慮して適時選択すればよく、通常、水、エチレングリコール、エタノール等が挙げられ、好ましくは水である。 As the polymerization inhibitor for vinyl acetate of the present invention, a polymerization inhibitor using the organic acids of the present invention alone or in combination of two or more, and a single or two or more of the organic acids of the present invention dissolved in a solvent are used. There is a polymerization inhibitor, and any of them may be used. The concentration of the organic acid in the polymerization inhibitor in which the organic acid of the present invention is dissolved in a solvent is not uniformly determined, and may be appropriately determined in consideration of the target process, the used organic acid and its water-soluble salt. Generally, the concentration is 1 to 50% by weight. The solvent to be used may be selected in a timely manner in consideration of the target process and the organic acid used and its water-soluble salt. Usually, water, ethylene glycol, ethanol and the like can be mentioned, and water is preferred.
本発明の重合抑制剤の製造は、特に限定されるものではなく、一般的な方法により製造することができる。具体的には、本発明の有機酸類の1種以上を撹拌下、溶剤に添加して均一溶液に調製して得られる。また、本発明の酢酸ビニルの重合抑制剤に従来より使用されている他の重合抑制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。 The production of the polymerization inhibitor of the present invention is not particularly limited, and can be produced by a general method. Specifically, it can be obtained by preparing one or more organic acids of the present invention in a solvent with stirring to prepare a homogeneous solution. Moreover, the other polymerization inhibitor conventionally used for the polymerization inhibitor of the vinyl acetate of this invention can be mix | blended in the range which does not prevent the effect of this invention.
本発明の重合抑制剤の添加量は、通常、酢酸ビニルの工程の運転状況、酢酸ビニルの重合抑制の要求度、経済的観点などを加味して決定されもので一律に決めることはできないが、通常、酢酸ビニルを含む工程液中の酢酸ビニルに対して、本発明の重合抑制剤中の有機酸類として０．０５〜１０００ｐｐｍ、好ましくは０．５〜１００ｐｐｍである。本発明の重合抑制剤中の有機酸類としての添加量が０．０５ｐｐｍより少ないと効果が十分に発揮されない場合があり、本発明の重合抑制剤中の有機酸類としての添加量が１０００ｐｐｍより多くす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 amount of addition of the polymerization inhibitor of the present invention is usually determined in consideration of the operation status of the vinyl acetate process, the degree of vinyl acetate polymerization suppression requirement, an economic viewpoint, etc., and cannot be determined uniformly. Usually, it is 0.05-1000 ppm as an organic acid in the polymerization inhibitor of this invention with respect to vinyl acetate in the process liquid containing vinyl acetate, Preferably it is 0.5-100 ppm. If the addition amount as organic acids in the polymerization inhibitor of the present invention is less than 0.05 ppm, the effect may not be sufficiently exerted, and the addition amount as organic acids in the polymerization inhibitor of the present invention is more than 1000 ppm. This does not prevent anything, but it does not improve the effect commensurate with the amount added, which may be disadvantageous from an economic standpoint.
本発明の酢酸ビニルの重合抑制方法（以下、「本発明の重合抑制方法」とする。）は、酢酸ビニルの製造工程、精製工程、貯蔵およびその輸送工程において、酢酸ビニルを含む当該工程液に一般式（１）で表されるα−ヒドロキシカルボン酸およびアスコルビン酸からなる有機酸および／又はその水溶性塩から選ばれた1種以上を添加することによって、酢酸ビニルの重合抑制および重合によって生じる汚れの発生を抑制する酢酸ビニルの重合抑制方法である。 The method for inhibiting the polymerization of vinyl acetate of the present invention (hereinafter referred to as “the method of inhibiting polymerization of the present invention”) is applied to the process liquid containing vinyl acetate in the production process, purification process, storage and transport process of vinyl acetate. By adding one or more selected from an organic acid composed of α-hydroxycarboxylic acid and ascorbic acid represented by the general formula (1) and / or a water-soluble salt thereof, it is caused by polymerization inhibition and polymerization of vinyl acetate. This is a method for inhibiting the polymerization of vinyl acetate to suppress the occurrence of dirt.
本発明の重合抑制方法における有機酸類の添加箇所は、酢酸ビニルの製造工程や精製工程の運転状況、酢酸ビニルの重合の程度および汚れの程度等を考慮して適宜選択されるが、通常、障害が発生している箇所および酢酸ビニルの重合が生じる箇所の手前、酢酸ビニルの重合により生じた重合物が付着し汚れとなる箇所の手前である。具体的には、酢酸ビニル製造工程の反応塔手前の原料フィード液および循環ライン液、精製工程における精製塔のフィード液、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。 In the polymerization inhibiting method of the present invention, the addition site of the organic acid is appropriately selected in consideration of the operating conditions of the vinyl acetate production process and the purification process, the degree of polymerization of vinyl acetate, the degree of contamination, etc. This is before the location where the occurrence of the polymerization occurs and the location where the polymerization of vinyl acetate occurs, and the location before the location where the polymer produced by the polymerization of vinyl acetate adheres and becomes dirty. Specifically, it is added to raw material feed liquid and circulation line liquid before the reaction tower in the vinyl acetate production process, purification tower feed liquid in the purification process, and storage equipment such as storage tanks, storage tanks, and transfer tanks during storage and transportation. Is done.
本発明の重合抑制方法における有機酸類の添加量は、通常、対象とする酢酸ビニルの工程の運転状況、酢酸ビニルの重合抑制の要求度、経済的観点などを加味して決定されもので一律に決めることはできないが、通常、酢酸ビニルを含む工程液中の酢酸ビニルに対して０．０５〜１０００ｐｐｍ、好ましくは０．５〜１００ｐｐｍである。有機酸類としての添加量が０．０５ｐｐｍより少ないと効果が十分に発揮されない場合があり、有機酸類としての添加量が１０００ｐｐｍより多くす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 amount of organic acids added in the polymerization inhibition method of the present invention is generally determined in consideration of the operational status of the target vinyl acetate process, the degree of vinyl acetate polymerization inhibition, and an economic viewpoint. Although it cannot be determined, it is usually 0.05 to 1000 ppm, preferably 0.5 to 100 ppm based on vinyl acetate in the process liquid containing vinyl acetate. If the addition amount as an organic acid is less than 0.05 ppm, the effect may not be sufficiently exerted, and increasing the addition amount as an organic acid above 1000 ppm does not prevent anything, but the effect commensurate with the addition amount There is no improvement, which may be disadvantageous from an economic point of view.
本発明の重合抑制方法における有機酸類の添加方法は、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、ある特定箇所に一括添加するか、あるいはいくつかの箇所に分けて添加するなどの方法が適宜選択される。 The addition method of the organic acids in the polymerization inhibition method of the present invention is not particularly limited, and is added using a normal chemical injection pump, and is added to a specific location at once, or divided into several locations. A method such as addition is appropriately selected.
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.
（有機酸）
A：２−ヒドロキシ−４−メチルペンタン酸（試薬、東京化成工業株式会社製）
B：２−ヒドロキシブタン酸（試薬、東京化成工業株式会社製）
C：２−ヒドロキシヘキサン酸（試薬、東京化成工業株式会社製）
D：２−ヒドロキシ−３，３−ジメチルブタン酸（試薬、東京化成工業株式会社製）
E：２−ヒドロキシ−２−メチルプロパン酸（試薬、東京化成工業株式会社製）
F：アスコルビン酸（試薬、東京化成工業株式会社製）
G：エリソルビン酸（試薬、東京化成工業株式会社製）
H：グリセリン酸（試薬、東京化成工業株式会社製）
I：グリコール酸（試薬、東京化成工業株式会社製）
J：乳酸（試薬、東京化成工業株式会社製）
K：酒石酸（試薬、東京化成工業株式会社製）
L：クエン酸（試薬、東京化成工業株式会社製）
M：リンゴ酸（試薬、東京化成工業株式会社製）
N：グルコン酸（試薬、東京化成工業株式会社製）
O：ヘプトン酸（試薬、東京化成工業株式会社製）
(Organic acid)
A: 2-hydroxy-4-methylpentanoic acid (reagent, manufactured by Tokyo Chemical Industry Co., Ltd.)
B: 2-hydroxybutanoic acid (reagent, manufactured by Tokyo Chemical Industry Co., Ltd.)
C: 2-hydroxyhexanoic acid (reagent, manufactured by Tokyo Chemical Industry Co., Ltd.)
D: 2-hydroxy-3,3-dimethylbutanoic acid (reagent, manufactured by Tokyo Chemical Industry Co., Ltd.)
E: 2-hydroxy-2-methylpropanoic acid (reagent, manufactured by Tokyo Chemical Industry Co., Ltd.)
F: Ascorbic acid (reagent, manufactured by Tokyo Chemical Industry Co., Ltd.)
G: Erythorbic acid (reagent, manufactured by Tokyo Chemical Industry Co., Ltd.)
H: Glyceric acid (reagent, manufactured by Tokyo Chemical Industry Co., Ltd.)
I: Glycolic acid (reagent, manufactured by Tokyo Chemical Industry Co., Ltd.)
J: Lactic acid (reagent, manufactured by Tokyo Chemical Industry Co., Ltd.)
K: Tartaric acid (reagent, manufactured by Tokyo Chemical Industry Co., Ltd.)
L: Citric acid (reagent, manufactured by Tokyo Chemical Industry Co., Ltd.)
M: Malic acid (reagent, manufactured by Tokyo Chemical Industry Co., Ltd.)
N: Gluconic acid (reagent, manufactured by Tokyo Chemical Industry Co., Ltd.)
O: Heptonic acid (reagent, manufactured by Tokyo Chemical Industry Co., Ltd.)
〔重合抑制試験１〕
（試験液の調整）
２００ｇの酢酸ビニルを５００ｍｌの三つ口フラスコに入れ、６５℃のオイルバスに浸漬した後、５０ｍｌ／分の割合で圧縮空気を導入し、１時間加熱攪拌した。次ぎに三つ口フラスコ内の酢酸ビニル１００ｇを取り出し、別の三つ口フラスコに入れ、所定量の有機酸を添加し、窒素ガスを５０ｍＬ／分の割合で導入しながら、６５℃にて８時間、加熱還流した。５時間後、反応液約５ｇを採取し精秤した後、ヘキサン５０ｍｌに溶解させ、発生したポリマーを析出させた。ポリマーを１μｍガラス繊維瀘紙〔ミリポア社（Ｍｉｌｌｉｐｏｒｅ Ｃｏｒｐ．）製〕で瀘別し、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]
(Adjustment of test solution)
200 g of vinyl acetate was placed in a 500 ml three-necked flask, immersed in an oil bath at 65 ° C., compressed air was introduced at a rate of 50 ml / min, and the mixture was heated and stirred for 1 hour. Next, 100 g of vinyl acetate in the three-necked flask is taken out, put into another three-necked flask, a predetermined amount of organic acid is added, and nitrogen gas is introduced at a rate of 50 mL / min. Heated at reflux for hours. After 5 hours, about 5 g of the reaction solution was collected and precisely weighed, and then dissolved in 50 ml of hexane to precipitate the generated polymer. The polymer was separated by 1 μm glass fiber paper (Millipore Corp.), and the produced polymer was separated. 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.
Claims (4)
The method for inhibiting vinyl acetate polymerization according to claim 3, wherein 0.05 to 1000 ppm of the organic acid and / or water-soluble salt thereof is added to the amount of vinyl acetate in the process liquid.
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| JP2004252080A JP2006069916A (en) | 2004-08-31 | 2004-08-31 | Polymerization inhibitor for vinyl acetate and polymerization-inhibiting method |
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| JP2006069916A true JP2006069916A (en) | 2006-03-16 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006232874A (en) * | 2005-02-22 | 2006-09-07 | Hakuto Co Ltd | Polymerization inhibitor composition and polymerization-inhibiting method for vinyl acetate |
| WO2012058196A1 (en) * | 2010-10-28 | 2012-05-03 | Celanese International Corporation | Methods for producing a vinyl acetate composition having a low impurity content |
| CN111777697A (en) * | 2019-04-04 | 2020-10-16 | 应急管理部化学品登记中心 | Polymerization inhibitor for vinyl acetate solution and method of use |
-
2004
- 2004-08-31 JP JP2004252080A patent/JP2006069916A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006232874A (en) * | 2005-02-22 | 2006-09-07 | Hakuto Co Ltd | Polymerization inhibitor composition and polymerization-inhibiting method for vinyl acetate |
| JP4484726B2 (en) * | 2005-02-22 | 2010-06-16 | 伯東株式会社 | Polymerization inhibitor composition for vinyl acetate and polymerization inhibition method |
| WO2012058196A1 (en) * | 2010-10-28 | 2012-05-03 | Celanese International Corporation | Methods for producing a vinyl acetate composition having a low impurity content |
| CN103237784A (en) * | 2010-10-28 | 2013-08-07 | 国际人造丝公司 | Methods for producing a vinyl acetate composition having a low impurity content |
| US9193663B2 (en) | 2010-10-28 | 2015-11-24 | Celanese International Corporation | Methods for producing a vinyl acetate composition having a low impurity content |
| CN103237784B (en) * | 2010-10-28 | 2015-11-25 | 国际人造丝公司 | For the production of the method for vinyl acetate composition with low impurity content |
| CN111777697A (en) * | 2019-04-04 | 2020-10-16 | 应急管理部化学品登记中心 | Polymerization inhibitor for vinyl acetate solution and method of use |
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