JPH06345681A - Method for inhibiting (meth)acrylic acid or ester thereof - Google Patents
Method for inhibiting (meth)acrylic acid or ester thereofInfo
- Publication number
- JPH06345681A JPH06345681A JP6071008A JP7100894A JPH06345681A JP H06345681 A JPH06345681 A JP H06345681A JP 6071008 A JP6071008 A JP 6071008A JP 7100894 A JP7100894 A JP 7100894A JP H06345681 A JPH06345681 A JP H06345681A
- Authority
- JP
- Japan
- Prior art keywords
- polymerization
- acrylic acid
- meth
- ester
- polymerization inhibitor
- 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.)
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は（メタ）アクリル酸モノ
マーおよび（メタ）アクリル酸エステルモノマー（以下
（メタ）アクリル酸およびそのエステルと省略する）の
重合防止方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for preventing polymerization of a (meth) acrylic acid monomer and a (meth) acrylic acid ester monomer (hereinafter abbreviated as (meth) acrylic acid and its ester).
【０００２】[0002]
【従来の技術】（メタ）アクリル酸およびそのエステル
は光や熱によって自然重合し易い性質を持つことは一般
に知られている。従って（メタ）アクリル酸およびその
エステルには保存中の重合を防止するために、種々の重
合防止剤が単独あるいは数種組み合わされてモノマー中
に添加されている。2. Description of the Related Art It is generally known that (meth) acrylic acid and its esters have a property of being easily spontaneously polymerized by light or heat. Therefore, in order to prevent polymerization during storage, various polymerization inhibitors are added to the (meth) acrylic acid and its ester, either alone or in combination with each other, in the monomer.
【０００３】上記重合防止剤の一つとしてＮ−オキシル
化合物を使用することが試みられている。例えば、特公
昭45−1054号公報には、アクリル酸の安定化剤として第
３ブチルニトロオキシドまたは2,2,6,6-テトラメチル-4
- ヒドロキシピペリジン-1-オキシル等のＮ−オキシラ
ジカルを単独で用い、ハイドロキノン、フェノチアジ
ン、塩化第二銅等の従来公知のものより優れた重合防止
効果を示すことが開示されており、特公昭54−3853号公
報には、有機溶媒中で酸素含有ガスを用いてメタクロレ
インからメタクリル酸を製造する際の重合抑制剤とし
て、2,2,6,6-テトラメチル-4- ヒドロキシピペリジン-1
- オキシル、または2,2,6,6-テトラメチルピペリジン-1
- オキシルを用いる方法が開示されている。Attempts have been made to use N-oxyl compounds as one of the above polymerization inhibitors. For example, JP-B-45-1054 discloses that tert-butyl nitroxide or 2,2,6,6-tetramethyl-4 as a stabilizer of acrylic acid.
-Hydroxypiperidine-1-oxyl and other N-oxy radicals have been disclosed to exhibit superior polymerization-inhibiting effect to hydroquinone, phenothiazine, cupric chloride, etc. -3853, 2,2,6,6-tetramethyl-4-hydroxypiperidine-1 as a polymerization inhibitor when producing methacrylic acid from methacrolein using an oxygen-containing gas in an organic solvent.
-Oxyl or 2,2,6,6-tetramethylpiperidine-1
-A method using oxyl is disclosed.
【０００４】また、特公昭58-46496号公報には2,2,5,5-
テトラメチル-3- オキソピロリジン-1- オキシル、2,2,
6,6-テトラメチル-4- アセトキシピペリジン-1- オキシ
ル等の化合物を用いる方法が開示されている。さらに、
中国特許CN1052847Aにはアクリル酸およびアクリル酸エ
ステル類の重合防止方法として2,2,6,6-テトラメチル-4
- ヒドロキシピペリジン-1- オキシルの単独使用または
ハイドロキノンとの併用時の重合防止効果について開示
があり、ジブチルジチオカルバミン酸銅塩とハイドロキ
ノンを併用するよりも効果が高いことを示している。Further, Japanese Patent Publication No. 58-46496 discloses 2,2,5,5-
Tetramethyl-3-oxopyrrolidine-1-oxyl, 2,2,
A method using a compound such as 6,6-tetramethyl-4-acetoxypiperidine-1-oxyl is disclosed. further,
Chinese Patent CN1052847A describes 2,2,6,6-tetramethyl-4 as a method for preventing polymerization of acrylic acid and acrylates.
-Hydroxypiperidine-1-oxyl is disclosed as a polymerization inhibitory effect when used alone or in combination with hydroquinone, and it is shown to be more effective than the combined use of dibutyldithiocarbamic acid copper salt and hydroquinone.
【０００５】しかしながら、本発明者等が上記Ｎ−オキ
シル化合物単独またはＮ−オキシル化合物をハイドロキ
ノンと併用した重合防止剤系について検討した結果、以
下に示すような条件の場合はその重合防止効果に問題が
あることがわかった。However, as a result of investigations by the present inventors on a polymerization inhibitor system in which the above N-oxyl compound alone or an N-oxyl compound is used in combination with hydroquinone, the polymerization prevention effect is problematic under the following conditions. I found out that there is.
【０００６】すなわち、接触気相反応によって（メタ）
アクリル酸を製造する際の蒸留工程では、（メタ）アク
リル酸水溶液を共沸分離塔（水分離塔）で蒸留するが、
この時のフィード組成には水、酢酸およびアルデヒド類
が含まれていて（メタ）アクリル酸の重合が極めて起こ
り易くなっている。このため、上記の重合防止剤を通常
の添加量で使用しても防止効果は発現せず、蒸留中にポ
ップコーンポリマーや粘性ポリマーが発生して、蒸留塔
を含む製造装置の長期連続操業が不可能になるという問
題が起こっている。また、重合防止効果を発現させよう
とすれば、多量の重合防止剤が必要となり、実装置での
使用は困難であった。That is, by the catalytic gas phase reaction (meta)
In the distillation step for producing acrylic acid, the (meth) acrylic acid aqueous solution is distilled in the azeotropic separation column (water separation column),
At this time, the feed composition contains water, acetic acid and aldehydes, so that the polymerization of (meth) acrylic acid is extremely likely to occur. Therefore, even if the above-mentioned polymerization inhibitor is used in a usual addition amount, the preventing effect is not exhibited, popcorn polymer or viscous polymer is generated during the distillation, and the long-term continuous operation of the manufacturing apparatus including the distillation column is unsuccessful. The problem is that it will be possible. Further, if an attempt is made to exhibit a polymerization inhibitory effect, a large amount of a polymerization inhibitor is required, and it is difficult to use it in an actual device.
【０００７】[0007]
【発明が解決しようとする課題】本発明は上記事情に着
目してなされたものであって、（メタ）アクリル酸およ
びそのエステルが重合し易い工程であっても少量で重合
防止効果を発現し得る重合防止方法を見出すことを目的
とする。DISCLOSURE OF THE INVENTION The present invention has been made in view of the above circumstances. Even in a step where (meth) acrylic acid and its ester are easily polymerized, a small amount of the effect of preventing polymerization is exhibited. The purpose is to find a method of preventing polymerization that is obtained.
【０００８】[0008]
【課題を解決するための手段】上記目的を達成した本発
明の方法は、（メタ）アクリル酸およびそのエステルの
重合防止剤として、 2,2,6,6−テトラメチルピペリジノ
オキシル、 4−ヒドロキシ−2,2,6,6 −テトラメチルピ
ペリジノオキシルおよび4,4',4”−トリス−(2,2,6,6−
テトラメチルピペリジノオキシル）フォスファイトより
なる群から選択される１種以上のＮ−オキシル化合物
と、ハイドロキノンおよびメトキノンよりなる群から選
択される１種以上のフェノール化合物と、フェノチアジ
ン化合物を用いるところに要旨を有する。Means for Solving the Problems The method of the present invention which has achieved the above-mentioned object, comprises using 2,2,6,6-tetramethylpiperidinooxyl, 4) as a polymerization inhibitor of (meth) acrylic acid and its ester. -Hydroxy-2,2,6,6-tetramethylpiperidinooxyl and 4,4 ', 4 "-tris- (2,2,6,6-
Where one or more N-oxyl compounds selected from the group consisting of tetramethylpiperidinooxyl) phosphite, one or more phenol compounds selected from the group consisting of hydroquinone and metoquinone, and a phenothiazine compound are used. Have a gist.
【０００９】[0009]
【作用】本発明の重合防止方法は、重合防止剤として特
定のＮ−オキシル化合物とフェノール化合物とフェノチ
アジン化合物を併せて用いることが必須要件である。こ
れらの化合物は単独でも重合防止効果を有するが不充分
であり、またいずれか２成分を併用しても必ずしも充分
な重合防止効果は得られていない。本発明者らは、重合
防止剤を、特定のＮ−オキシル化合物とフェノール化合
物とフェノチアジン化合物の３成分系とすることによ
り、これまで単独あるいは２成分系では得られなかった
様な顕著な重合防止効果が相乗効果として現れることを
見出し、本発明に至ったものである。以下、本発明を詳
細に説明する。In the method for preventing polymerization of the present invention, it is essential that a specific N-oxyl compound, a phenol compound and a phenothiazine compound are used together as a polymerization inhibitor. These compounds alone have a polymerization inhibitory effect but are insufficient, and even if any two components are used in combination, a sufficient polymerization inhibitory effect is not always obtained. The inventors of the present invention use a three-component system of a specific N-oxyl compound, a phenol compound and a phenothiazine compound as the polymerization inhibitor, so that a remarkable polymerization inhibition which has not been obtained by a single or two-component system up to now has been achieved. The inventors have found that the effects appear as a synergistic effect, and have reached the present invention. Hereinafter, the present invention will be described in detail.
【００１０】本発明ではＮ−オキシル化合物として良好
な重合防止効果を与え得る 2,2,6,6−テトラメチルピペ
リジノオキシル、 4−ヒドロキシ−2,2,6,6 −テトラメ
チルピペリジノオキシル、4,4',4”−トリス−(2,2,6,6
−テトラメチルピペリジノオキシル）フォスファイトの
うち１種または２種以上を用いる。特に、Ｎ−オキシル
化合物として2,2,6,6 −テトラメチルピペリジノオキシ
ル、または4 −ヒドロキシ−2,2,6,6 −テトラメチルピ
ペリジノオキシルを用いた場合には、成分中に金属を含
まない安定剤系となるため、安定剤による設備の金属腐
食の恐れがなくなり、廃液の処理も容易になる。In the present invention, 2,2,6,6-tetramethylpiperidinooxyl and 4-hydroxy-2,2,6,6-tetramethylpiperidine which can give a good polymerization inhibitory effect as an N-oxyl compound. Nooxyl, 4,4 ', 4 "-tris- (2,2,6,6
One or more of tetramethylpiperidinooxyl) phosphite are used. In particular, when 2,2,6,6-tetramethylpiperidinooxyl or 4-hydroxy-2,2,6,6-tetramethylpiperidinooxyl is used as the N-oxyl compound, Since it is a stabilizer system containing no metal, there is no fear of metal corrosion of the equipment due to the stabilizer, and the waste liquid can be easily treated.
【００１１】本発明で用いられるフェノール化合物とし
ては、ハイドロキノン、メトキノン（ｐ−メトキシフェ
ノール）を挙げることができる。特にメトキノンは、Ｎ
−オキシル化合物およびフェノチアジン化合物と組合せ
て使用した際の重合防止効果がハイドロキノンより優れ
ているため好ましい。また、これらのフェノール化合物
は２種を併用してもよい。Examples of the phenol compound used in the present invention include hydroquinone and metoquinone (p-methoxyphenol). Especially, methquinone is N
-It is preferable because it has a higher polymerization inhibiting effect than hydroquinone when used in combination with an oxyl compound and a phenothiazine compound. Also, two or more of these phenol compounds may be used in combination.
【００１２】本発明で用いられるフェノチアジン化合物
としては、フェノチアジン、ビス−（α−メチルベンジ
ル）フェノチアジン、3,7 −ジオクチルフェノチアジ
ン、ビス−（α−ジメチルベンジル）フェノチアジン等
を挙げることができ、これらの中でも特にフェノチアジ
ンが好適に使用される。これらのフェノチアジン化合物
は２種以上を併用してもよい。Examples of the phenothiazine compound used in the present invention include phenothiazine, bis- (α-methylbenzyl) phenothiazine, 3,7-dioctylphenothiazine and bis- (α-dimethylbenzyl) phenothiazine. Among them, phenothiazine is particularly preferably used. Two or more kinds of these phenothiazine compounds may be used in combination.
【００１３】本発明では、上記Ｎ−オキシル化合物とフ
ェノール化合物とフェノチアジン化合物の３成分の重合
防止剤を用いることによって顕著な重合防止効果が達成
できる。必要に応じ分子状酸素を併用すれば重合防止効
果がさらに向上し、製造装置の長期連続運転が可能にな
る。In the present invention, a remarkable polymerization inhibiting effect can be achieved by using the three-component polymerization inhibitor of the N-oxyl compound, the phenol compound and the phenothiazine compound. If necessary, molecular oxygen may be used in combination to further improve the polymerization prevention effect and enable long-term continuous operation of the production apparatus.
【００１４】本発明の重合防止方法は、ビニル化合物の
中でも特に重合しやすい（メタ）アクリル酸およびその
エステルに好適に用いることができる。アクリル酸エス
テルとしては、アクリル酸メチル、アクリル酸エチル、
アクリル酸ブチル、アクリル酸２−エチルヘキシル、ア
クリル酸２−ヒドロキシエチル、アクリル酸２−ヒドロ
キシプロピル等が適用対象として挙げられ、メタクリル
酸エステルとしては、メタクリル酸メチル、メタクリル
酸ブチル、メタクリル酸２−ヒドロキシエチル、メタク
リル酸２−ヒドロキシプロピル等が適用対象として挙げ
られる。The method for preventing polymerization of the present invention can be preferably used for (meth) acrylic acid and its ester which are particularly easily polymerized among vinyl compounds. As the acrylate ester, methyl acrylate, ethyl acrylate,
Butyl acrylate, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate and the like can be mentioned as application targets, and as the methacrylic acid ester, methyl methacrylate, butyl methacrylate, 2-hydroxymethacrylic acid can be mentioned. Examples of applicable substances include ethyl and 2-hydroxypropyl methacrylate.
【００１５】重合防止方法としては、例えば、接触気相
酸化反応で（メタ）アクリル酸を製造する場合に関して
説明すれば、（メタ）アクリル酸の精留塔、（メタ）ア
クリル酸と溶剤の分離塔、（メタ）アクリル酸と酢酸等
の軽沸分との分離塔等の諸蒸留工程、アクロレインやメ
タクロレイン等の軽沸分のストリッパー等の蒸留操作を
含む諸工程において、上記重合防止剤を（メタ）アクリ
ル酸と共存させれば良い。As a method of preventing polymerization, for example, the case of producing (meth) acrylic acid by a catalytic gas phase oxidation reaction will be explained. As a rectification column of (meth) acrylic acid, separation of (meth) acrylic acid and solvent. In the column, various distillation steps such as a column for separating (meth) acrylic acid from light boiling components such as acetic acid, and in various steps including distillation operations such as strippers of light boiling components such as acrolein and methacrolein, the above polymerization inhibitor is added. It may be allowed to coexist with (meth) acrylic acid.
【００１６】本発明の重合防止方法は、３成分の重合防
止剤を上記諸工程において添加すれば良く、添加方法は
特に限定されない。固体または粉体等の形で直接添加し
てもよいし、他の有機溶剤の溶液や水溶液として添加し
ても良い。また、添加時期についても特に限定されず、
３成分を個別に、あるいは同時に、例えば一つの溶液の
形で添加しても良い。例えば、前記（メタ）アクリル酸
の製造時の蒸留工程等であれば、供給液や還流液に溶か
して前記諸工程中へ導入すれば良い。In the method for preventing polymerization of the present invention, a three-component polymerization inhibitor may be added in the above steps, and the addition method is not particularly limited. It may be added directly in the form of solid or powder, or may be added as a solution or aqueous solution of another organic solvent. Also, the addition timing is not particularly limited,
The three components may be added individually or simultaneously, for example in the form of one solution. For example, in the case of a distillation step during the production of the (meth) acrylic acid, it may be dissolved in a supply liquid or a reflux liquid and introduced into the various steps.
【００１７】使用される重合防止剤の量は、操作条件に
応じて適宜調整され、特に限定はされないが、上述した
３成分の重合防止剤の総量が、（メタ）アクリル酸およ
びそのエステルの蒸発蒸気量に対して２〜1000ppm （重
量基準）とするのが好ましい。個々の重合防止剤の好ま
しい使用量は、Ｎ−オキシル化合物の場合には該モノマ
ーの蒸発蒸気量に対し0.1 〜100ppm、フェノール化合物
の場合には該モノマーの蒸発蒸気量に対し１〜500ppm、
フェノチアジン化合物の場合には該モノマーの蒸発蒸気
量に対し１〜500ppmである。特にフェノール化合物とフ
ェノチアジン化合物の量は同程度であることが望まし
い。The amount of the polymerization inhibitor used is appropriately adjusted according to the operating conditions and is not particularly limited, but the total amount of the above-mentioned three-component polymerization inhibitor is the evaporation amount of (meth) acrylic acid and its ester. The amount of steam is preferably 2 to 1000 ppm (weight basis). The preferred amount of each polymerization inhibitor used is 0.1 to 100 ppm based on the amount of vaporized vapor of the monomer in the case of N-oxyl compound, and 1 to 500 ppm based on the amount of vaporized vapor of the monomer in the case of phenol compound.
In the case of a phenothiazine compound, it is 1 to 500 ppm with respect to the amount of vaporized vapor of the monomer. Particularly, it is desirable that the amounts of the phenol compound and the phenothiazine compound are about the same.
【００１８】ここでいう蒸発蒸気量とは、蒸留塔のリボ
イラーから加えられた熱量に相当して、塔底から蒸発す
るモノマーの蒸気の総量を意味する。重合防止剤の投入
基準を決定する上で重要な因子となる数字である。The amount of vaporized vapor as used herein means the total amount of vapor of the monomer vaporized from the bottom of the column, which corresponds to the amount of heat added from the reboiler of the distillation column. It is a number that is an important factor in determining the input standard of the polymerization inhibitor.
【００１９】なお、必要に応じて用いられる分子状酸素
については、エアーバブリング等により、（メタ）アク
リル酸およびそのエステルに直接混入させても良いし、
あるいは、他の溶媒に溶け込んだ状態で（メタ）アクリ
ル酸およびそのエステルに間接的に混入させても良い。
蒸留塔やストリッパーの塔底および／またはリボイラー
からガス状で送り込めばエアーバブリングが簡単に製造
工程に組み込める。分子状酸素は、（メタ）アクリル酸
の蒸発蒸気量に対して0.1 〜1.0 容量％程度投入するこ
とが望ましい。本発明の重合防止方法は、（メタ）アク
リル酸およびそのエステルの輸送時や貯蔵時にも優れた
重合防止効果を発揮する。The molecular oxygen used as required may be directly mixed with (meth) acrylic acid and its ester by air bubbling or the like,
Alternatively, it may be indirectly mixed with (meth) acrylic acid and its ester in a state of being dissolved in another solvent.
Air bubbling can be easily incorporated into the manufacturing process by sending it in gaseous form from the bottom of the distillation column or stripper and / or the reboiler. It is desirable to add molecular oxygen in an amount of about 0.1 to 1.0% by volume with respect to the amount of evaporated vapor of (meth) acrylic acid. INDUSTRIAL APPLICABILITY The polymerization preventing method of the present invention exerts an excellent polymerization preventing effect during the transportation and storage of (meth) acrylic acid and its ester.
【００２０】[0020]
【実施例】以下実施例によって本発明をさらに詳述する
が、下記実施例は本発明を制限するものではなく、前・
後記の趣旨を逸脱しない範囲で変更実施することは全て
本発明の技術範囲に包含される。なお下記実施例および
比較例中の単位ppm はいずれも重量を基準とする。The present invention will be described in more detail with reference to the following examples, but the following examples do not limit the present invention.
All modifications and implementations that do not depart from the spirit of the description below are included in the technical scope of the present invention. The unit ppm in the following examples and comparative examples are based on weight.
【００２１】実施例１ 予め蒸留により重合防止剤を除去したアクリル酸を試験
ブランク液とした。このブランク液２mlを試験管に取り
表１に示した組成および濃度（表中の単位はppm であ
る。以下同様）の重合防止剤を添加して調整液とした。
No. １〜１１は比較実験例である。次いで試験管内を減
圧にした後、 100℃に保ったオイルバスに浸漬して、目
視にて重合時間を測定した。その結果を表１に示す。な
お、以下の実施例では化合物名を下記の通り省略して示
す。Example 1 Acrylic acid from which a polymerization inhibitor was previously removed by distillation was used as a test blank solution. 2 ml of this blank solution was placed in a test tube, and a polymerization inhibitor having the composition and concentration shown in Table 1 (unit in the table is ppm; the same applies hereinafter) was added to prepare a preparation solution.
No. 1 to 11 are comparative experimental examples. Next, after decompressing the inside of the test tube, the test tube was immersed in an oil bath maintained at 100 ° C., and the polymerization time was measured visually. The results are shown in Table 1. In the following examples, compound names are abbreviated as follows.
【００２２】ＴＥＭＰＯ ： 2,2,6,6−テトラ
メチルピペリジノオキシル ４Ｈ−ＴＥＭＰＯ ： 4−ヒドロキシ−2,2,6,6 −テ
トラメチルピペリジノオキシル ＴＲＩＳ−ＴＥＭＰＯ： 4,4',4 ”−トリス−(2,2,6,6
−テトラメチルピペリジノオキシル）フォスファイト ＤＴＢＮＯ ：ジターシャリーブチルニトロオ
キシド ＨＱ ：ハイドロキノン ＭＱ ：メトキノン ＢＱ ：ベンゾキノン ＰＴＺ ：フェノチアジンTEMPO: 2,2,6,6-tetramethylpiperidinooxyl 4H-TEMPO: 4-hydroxy-2,2,6,6-tetramethylpiperidinooxyl TRIS-TEMPO: 4,4 ', 4 "-Tris- (2,2,6,6
-Tetramethylpiperidinooxyl) phosphite DTBNO: ditertiary butyl nitroxide HQ: hydroquinone MQ: metoquinone BQ: benzoquinone PTZ: phenothiazine
【００２３】[0023]
【表１】 [Table 1]
【００２４】表１から明らかな様に、重合防止剤が単独
系または２成分系の比較実験例No.１〜８はいずれも本
発明例のNo. １２〜１７に比べて重合時間が短く、重合
防止効果が劣っていることがわかる。特に本発明例のN
o. １４〜１５は重合防止剤の総量が少なくなっている
にもかかわらず、No. ５〜８に比べて重合時間が長くな
っている。従って３成分系のいずれか１成分が欠けても
重合時間が短くなり、３成分系での使用が好適であるこ
とがわかる。また、ＨＱやＭＱの代わりにＢＱを用いた
比較実験例No. ９や、Ｎ−オキシル化合物として本発明
範囲外のＤＴＢＮＯを用いた比較実験例No. １０〜１１
は、本発明例のNo. １２〜１３に比べて重合時間が短
く、３成分系であっても重合防止効果が劣っていること
がわかる。As is apparent from Table 1, the comparative experimental examples Nos. 1 to 8 in which the polymerization inhibitor was a single type or a two-component type had a shorter polymerization time than Nos. 12 to 17 of the present invention. It can be seen that the polymerization prevention effect is inferior. In particular N of the present invention example
o. 14 to 15 have a longer polymerization time than Nos. 5 to 8 although the total amount of the polymerization inhibitor is small. Therefore, even if any one component of the three-component system is lacking, the polymerization time becomes short, and it is understood that the use in the three-component system is suitable. Further, Comparative Experimental Example No. 9 using BQ instead of HQ or MQ and Comparative Experimental Example Nos. 10 to 11 using DTBNO outside the scope of the present invention as the N-oxyl compound.
It can be seen that, compared to Nos. 12 to 13 of the present invention, the polymerization time is shorter and the polymerization prevention effect is inferior even in the case of the three-component system.
【００２５】実施例２ 上部に留出管を備え、中央部に原料供給管を備えた充填
塔を用いてアクリル酸水溶液の共沸分離を行った。供給
原料としては、プロピレンの接触気相反応によって得ら
れた水を30重量％および酢酸を 2.5重量％含むアクリル
酸水溶液を用い、還流液としてメチルイソブチルケトン
を用い、操作圧160mmHg 、塔頂温度49℃、塔底温度97℃
の条件下で蒸留した。表２に示した量の重合防止剤を還
流液に添加溶解した形でカラム内に投入し、酸素ガスは
塔底部に供給した。重合防止剤および酸素の投入量基準
はアクリル酸の蒸発蒸気量に対する量である。定常状態
における塔底抜き出し液の組成は、アクリル酸97重量
％、酢酸 0.5重量％、その他2.5重量％であった。還流
液は留出油相をリサイクルして用いた。８時間の運転時
間において塔内に発生したポリマーを減圧乾燥して恒量
にした後測定して重合防止効果を見た。その結果を表２
に示す。Example 2 Aqueous acrylic acid solution was subjected to azeotropic separation using a packed column equipped with a distillation pipe in the upper part and a raw material supply pipe in the central part. As the feedstock, an acrylic acid aqueous solution containing 30% by weight of water and 2.5% by weight of acetic acid obtained by the catalytic gas phase reaction of propylene was used, methyl isobutyl ketone was used as a reflux liquid, an operating pressure of 160 mmHg, and a tower top temperature of 49 ℃, tower bottom temperature 97 ℃
Distilled under the conditions. The amount of the polymerization inhibitor shown in Table 2 was added to and dissolved in the reflux liquid and charged into the column, and oxygen gas was supplied to the bottom of the column. The amount of the polymerization inhibitor and oxygen added is based on the amount of evaporated vapor of acrylic acid. In the steady state, the composition of the column bottom withdrawal liquid was 97% by weight of acrylic acid, 0.5% by weight of acetic acid, and 2.5% by weight of others. The reflux liquid was used by recycling the distillate oil phase. The polymer generated in the tower during the operation time of 8 hours was dried under reduced pressure to a constant weight and then measured to see the polymerization inhibitory effect. The results are shown in Table 2.
Shown in.
【００２６】[0026]
【表２】 [Table 2]
【００２７】表２から明らかな様に３成分系のいずれか
１成分が欠けてもポリマーが多く発生しており、本発明
の重合防止方法を適用したNo. ２３〜２４は生成ポリマ
ー量が少ないことがわかる。As is apparent from Table 2, a large amount of polymer is generated even if any one component of the three-component system is lacking, and Nos. 23 to 24 to which the polymerization inhibiting method of the present invention is applied have a small amount of produced polymer. I understand.
【００２８】実施例３ 予め蒸留により重合防止剤を除去したメタクリル酸を試
験ブランク液とした。このブランク液２mlを試験管に取
り表３に示した組成および濃度の重合防止剤を添加して
調整液とした。No. ２５〜２７は比較実験例である。次
いで試験管内を減圧にした後、 130℃に保ったオイルバ
スに浸漬して、目視にて重合時間を測定した。その結果
を表３に示す。Example 3 Methacrylic acid from which the polymerization inhibitor was removed by distillation beforehand was used as a test blank solution. 2 ml of this blank solution was placed in a test tube and a polymerization inhibitor having the composition and concentration shown in Table 3 was added to prepare a preparation solution. No. 25-27 are comparative experimental examples. Next, after depressurizing the inside of the test tube, the test tube was immersed in an oil bath maintained at 130 ° C., and the polymerization time was visually measured. The results are shown in Table 3.
【００２９】[0029]
【表３】 [Table 3]
【００３０】表３から明らかな様に重合防止剤が２成分
系の比較実験例No. ２５〜２７はいずれも本発明例のN
o. ２８〜３１に比べて重合時間が短く、重合防止効果
が劣っていることがわかる。本発明例のNo. ２９および
３１は重合防止剤の総量が少なくなっているにもかかわ
らず、No. ２５〜２７に比べて重合時間が長くなってお
り、優れた重合防止効果を発揮した。As is apparent from Table 3, Comparative Experimental Examples No. 25 to 27, in which the polymerization inhibitor is a two-component system, are all N of the present invention.
It can be seen that the polymerization time is shorter than that of o. In Nos. 29 and 31 of the present invention, the total polymerization amount of the polymerization inhibitor was small, but the polymerization time was longer than that of Nos. 25 to 27, and the excellent polymerization prevention effect was exhibited.
【００３１】実施例４ 予め蒸留により重合防止剤を除去した下記アクリル酸エ
ステルを試験ブランク液とした。このブランク液３０ml
を試験管に取り表４に示した組成および濃度の重合防止
剤を添加して調整液とした。次いで試験管内を減圧にし
た後、下記温度に保持したオイルバスに浸漬しながら、
試料の液温を測定し、重合による発熱を開始した時間を
重合時間として表４に示した。Example 4 The following acrylic acid ester from which the polymerization inhibitor was removed by distillation beforehand was used as a test blank solution. 30 ml of this blank solution
Was placed in a test tube and a polymerization inhibitor having the composition and concentration shown in Table 4 was added to prepare a preparation liquid. Then, after reducing the pressure in the test tube, while immersing in an oil bath maintained at the following temperature,
The liquid temperature of the sample was measured, and the time when heat generation due to polymerization was started is shown in Table 4 as the polymerization time.
【００３２】なお、アクリル酸メチル（ＡＭ）のときの
オイルバス温度は70℃で、アクリル酸エチル（ＡＥ）の
ときは90℃、アクリル酸ブチル（ＡＢ）およびアクリル
酸オクチル（ＡＯ）のときのオイルバス温度は 120℃に
保持した。The oil bath temperature for methyl acrylate (AM) is 70 ° C., 90 ° C. for ethyl acrylate (AE), butyl acrylate (AB) and octyl acrylate (AO). The oil bath temperature was maintained at 120 ° C.
【００３３】[0033]
【表４】 [Table 4]
【００３４】表４から明らかな様に重合防止剤が２成分
系の比較実験例No. ３２〜３４はどの種類のアクリル酸
エステルにおいても、本発明例のNo. ３５〜３８に比べ
て重合時間が短く、重合防止効果が劣っていることがわ
かる。As is clear from Table 4, Comparative Experiment Nos. 32 to 34, in which the polymerization inhibitor is a two-component system, have a longer polymerization time than any of Nos. 35 to 38 of the present invention in any kind of acrylic acid ester. It can be seen that the value is short and the polymerization prevention effect is inferior.
【００３５】実施例５ 予め蒸留により重合防止剤を除去した下記メタクリル酸
エステルを試験ブランク液とした。このブランク液３０
mlを試験管に取り表５に示した組成および濃度の重合防
止剤を添加して調整液とした。実施例４と同様にして重
合時間を測定し表５に示した。なお、メタクリル酸メチ
ル（ＭＭＡ）のときのオイルバス温度は90℃で、メタク
リル酸ブチル（ＢＭＡ）のときは 120℃とした。Example 5 The following methacrylic acid ester from which the polymerization inhibitor was removed by distillation beforehand was used as a test blank solution. This blank solution 30
ml was placed in a test tube and the polymerization inhibitor having the composition and concentration shown in Table 5 was added to prepare a preparation liquid. The polymerization time was measured in the same manner as in Example 4 and is shown in Table 5. The oil bath temperature was 90 ° C. for methyl methacrylate (MMA) and 120 ° C. for butyl methacrylate (BMA).
【００３６】[0036]
【表５】 [Table 5]
【００３７】表５から明らかな様に重合防止剤が２成分
系の比較実験例No. ３９〜４１はいずれのメタクリル酸
エステルにおいても、本発明例のNo. ４２〜４５に比べ
て重合時間が短く、重合防止効果が劣っていることがわ
かる。As is clear from Table 5, in Comparative Experimental Examples Nos. 39 to 41 in which the polymerization inhibitor is a two-component system, the polymerization time is longer than that in Nos. 42 to 45 of the present invention in any methacrylic acid ester. It can be seen that it is short and the polymerization prevention effect is inferior.
【００３８】実施例６ 予め蒸留により重合防止剤を除去した下記（メタ）アク
リル酸エステルを試験ブランク液とした。このブランク
液３０mlを試験管に取り表６に示した組成および濃度の
重合防止剤を添加して調整液とした。次いで試験管内を
減圧にした後、100℃に保持したオイルバスに浸漬しな
がら、試料の液温を測定し、重合による発熱を開始した
時間を重合時間として表６に示した。 ＨＥＡ ：アクリル酸２−ヒドロキシエチル ＨＰＡ ：アクリル酸２−ヒドロキシプロピル ＨＥＭＡ：メタクリル酸２−ヒドロキシエチル ＨＰＭＡ：メタクリル酸２−ヒドロキシプロピルExample 6 The following (meth) acrylic acid ester from which the polymerization inhibitor was removed by distillation beforehand was used as a test blank solution. 30 ml of this blank solution was placed in a test tube and a polymerization inhibitor having the composition and concentration shown in Table 6 was added to prepare a preparation solution. Next, after the pressure inside the test tube was reduced, the liquid temperature of the sample was measured while immersed in an oil bath maintained at 100 ° C., and the time when heat generation due to polymerization was started is shown in Table 6 as the polymerization time. HEA: 2-hydroxyethyl acrylate HPA: 2-hydroxypropyl acrylate HEMA: 2-hydroxyethyl methacrylate HPMA: 2-hydroxypropyl methacrylate
【００３９】[0039]
【表６】 [Table 6]
【００４０】表６から明らかな様に本発明例の重合防止
効果が優れていることがわかる。 実施例７ 50段のステンレス製シーブトレイを段間隔 147mmで内装
し、上部に留出管、中央部に原料供給管を備えた内径 1
05mmの蒸留塔を使用し、アクリル酸水溶液の共沸分離の
連続運転を行った。重合防止剤成分として、4-ヒドロキ
シ-2,2,6,6- テトラメチルピペリジノオキシル(4H-TEMP
O)、ハイドロキノン(HQ)、フェノチアジン(PTZ) および
酸素ガスを用いた。4H-TEMPOを30ppm 、HQを100ppm、PT
Z を100ppm（いずれも対アクリル酸蒸発蒸気量）メチル
イソブチルケトンに添加溶解し塔頂から導入し、また酸
素は塔底部にアクリル酸蒸発蒸気量に対して0.3vol％供
給した。As is apparent from Table 6, the polymerization inhibiting effect of the examples of the present invention is excellent. Example 7 Inner diameter of 50 stages of stainless steel sieve trays with a step interval of 147 mm, a distillation pipe in the upper part, and a raw material supply pipe in the central part 1
Using a 05 mm distillation column, continuous operation of azeotropic separation of acrylic acid aqueous solution was performed. As a polymerization inhibitor component, 4-hydroxy-2,2,6,6-tetramethylpiperidinooxyl (4H-TEMP
O), hydroquinone (HQ), phenothiazine (PTZ) and oxygen gas were used. 4H-TEMPO 30ppm, HQ 100ppm, PT
Z was added to and dissolved in 100 ppm (both acrylic acid evaporation vapor amount) methyl isobutyl ketone and introduced from the top of the column, and oxygen was supplied to the column bottom at 0.3 vol% with respect to the acrylic acid evaporation vapor amount.
【００４１】供給原料としてプロピレンからの接触気相
酸化反応によって得られた水を30重量％、酢酸を2.5 重
量％含むアクリル酸を、また還流液としてメチルイソブ
チルケトンを用い、塔頂温度46℃、塔底温度97℃、塔頂
圧110mmHg 、塔底圧152mmHg、フィード段37段の条件下
供給液量10.58 l/hr、還流液量19.54 l/hr、塔底抜出し
量7.05 l/hr 、留出水相3.94 l/hr 、留出油相19.74 l/
hr、R/D ＝0.92（モル基準）で蒸留した。Acrylic acid containing 30% by weight of water and 2.5% by weight of acetic acid obtained by catalytic gas phase oxidation reaction from propylene was used as a feed material, and methyl isobutyl ketone was used as a reflux liquid. Tower bottom temperature 97 ° C, tower top pressure 110 mmHg, tower bottom pressure 152 mmHg, conditions of 37 feed stages Feed volume 10.58 l / hr, reflux volume 19.54 l / hr, bottom drawout 7.05 l / hr, distillate Water phase 3.94 l / hr, distillate oil phase 19.74 l / hr
Distilled at hr, R / D = 0.92 (molar basis).
【００４２】定常状態における塔底抜出し液組成は、ア
クリル酸97.2重量％、酢酸 0.5重量％、その他 2.3重量
％であり、留出水相組成は水90.8％、アクリル酸 0.4重
量％、酢酸 6.5重量％、メチルイソブチルケトン 2.3重
量％であり、留出油相組成はメチルイソブチルケトン8
6.7重量％、水 3.9重量％、アクリル酸 1.4重量％、酢
酸 6.5重量％、その他 1.5重量％であり、還流液は留出
油相をリサイクルして用いた。重合防止効果は、塔内の
圧損失、フラッディングまたは塔の解体点検によって確
認した。In the steady state, the composition of the bottom withdrawal liquid was 97.2% by weight of acrylic acid, 0.5% by weight of acetic acid and 2.3% by weight of others, and the composition of the distillate water phase was 90.8% of water, 0.4% by weight of acrylic acid and 6.5% by weight of acetic acid. %, Methyl isobutyl ketone 2.3 wt%, distillate oil phase composition is methyl isobutyl ketone 8
6.7% by weight, 3.9% by weight of water, 1.4% by weight of acrylic acid, 6.5% by weight of acetic acid, and 1.5% by weight of others, and the reflux liquid was used by recycling the distillate oil phase. The effect of preventing polymerization was confirmed by pressure loss in the tower, flooding, or disassembly inspection of the tower.
【００４３】この条件にて約14日間連続運転したところ
に常に安定した状態が得られ、運転停止後、蒸留塔内の
点検を行った結果においても重合物の発生は全く認めら
れなかった。Under these conditions, a stable state was always obtained after about 14 days of continuous operation, and after the operation was stopped, the distillation column was inspected, and no polymer was found to be generated.
【００４４】比較例１ 実施例７で使用した重合防止剤系からPTZ を除いて２成
分系にし、HQの投入量を200ppmにして重合防止剤の総量
を実施例７と同じにしたほかは実施例７と同様の条件で
実験を行った。この条件では運転開始より２日後に塔内
の圧損失が認められ運転を継続することが困難であっ
た。運転を停止し解体点検を実施したところ、塔内にポ
ップコーンポリマーの生成を認めた。このことからＮ−
オキシル化合物とフェノール化合物だけでは重合防止効
果が低いことがわかった。COMPARATIVE EXAMPLE 1 PTC was removed from the polymerization inhibitor system used in Example 7 to prepare a two-component system, the amount of HQ was set to 200 ppm, and the total amount of the polymerization inhibitors was the same as in Example 7. The experiment was conducted under the same conditions as in Example 7. Under these conditions, it was difficult to continue the operation because pressure loss inside the tower was observed 2 days after the start of operation. When the operation was stopped and a disassembly inspection was performed, the formation of popcorn polymer was confirmed in the tower. From this, N-
It was found that the oxyl compound and the phenol compound alone have a low polymerization inhibiting effect.
【００４５】比較例２ 実施例７で使用した重合防止剤系からHQを除いて２成分
系にし、PTZ の投入量を200ppmにして重合防止剤の総量
を実施例７と同じにしたほかは実施例７と同様の条件で
実験を行った。この条件では運転開始より４日後に塔内
の圧損失が認められ運転を継続することが困難であっ
た。運転を停止し解体点検を実施したところ、塔内にポ
ップコーンポリマーの生成を認めた。このことからＮ−
オキシル化合物とフェノチアジンだけでは重合防止効果
が低いことがわかった。Comparative Example 2 Except that HQ was removed from the polymerization inhibitor system used in Example 7 to prepare a two-component system, the amount of PTZ added was 200 ppm, and the total amount of the polymerization inhibitors was the same as in Example 7. The experiment was conducted under the same conditions as in Example 7. Under these conditions, pressure loss in the tower was observed 4 days after the start of operation, making it difficult to continue operation. When the operation was stopped and a disassembly inspection was performed, the formation of popcorn polymer was confirmed in the tower. From this, N-
It was found that the oxyl compound and phenothiazine alone had a low polymerization inhibiting effect.
【００４６】[0046]
【発明の効果】本発明の重合防止方法は以上の様に構成
されており、特定のＮ−オキシル化合物、フェノール化
合物およびフェノチアジン化合物の３成分を併用するこ
とによって、これらの化合物を単独でまたは２成分で用
いた場合に比べて重合防止効果が著しく向上し、（メ
タ）アクリル酸およびそのエステルが極めて重合しやす
い条件下でもこれらのモノマーの重合を未然に防止する
ことができるようになった。従って（メタ）アクリル酸
およびそのエステルの製造装置の長期連続運転を可能に
すると共に、（メタ）アクリル酸およびそのエステルの
輸送時や貯蔵時においても優れた重合防止効果を発揮す
るものである。The method for preventing polymerization of the present invention is constituted as described above, and by using together three components of a specific N-oxyl compound, a phenol compound and a phenothiazine compound, these compounds can be used alone or in combination with each other. The effect of preventing polymerization is remarkably improved as compared with the case where it is used as a component, and it has become possible to prevent the polymerization of these monomers even under the condition that (meth) acrylic acid and its ester are extremely easily polymerized. Therefore, it enables a long-term continuous operation of the production apparatus of (meth) acrylic acid and its ester, and exerts an excellent polymerization inhibiting effect during the transportation and storage of (meth) acrylic acid and its ester.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 赤沢 陽治 兵庫県姫路市網干区興浜字西沖992番地の １ 株式会社日本触媒姫路製造所内 (72)発明者 馬場 将夫 兵庫県姫路市網干区興浜字西沖992番地の １ 株式会社日本触媒姫路製造所内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Yoji Akazawa, 992, Nishioki, Nishihama, Aboshi-ku, Himeji-shi, Hyogo Prefecture 1 Inside Nihon Shatai Co., Ltd. Himeji Factory (72) Masao Baba, 992, Nishi-oki, Ohamaji, Aboshi-ku, Himeji, Hyogo Prefecture 1 Inside Nippon Shokubai Himeji Factory
Claims (1)
の重合防止剤として、 2,2,6,6−テトラメチルピペリジ
ノオキシル、 4−ヒドロキシ−2,2,6,6 −テトラメチル
ピペリジノオキシルおよび4,4',4”−トリス−(2,2,6,6
−テトラメチルピペリジノオキシル）フォスファイトよ
りなる群から選択される１種以上のＮ−オキシル化合物
と、ハイドロキノンおよびメトキノンよりなる群から選
択される１種以上のフェノール化合物と、フェノチアジ
ン化合物を用いることを特徴とする（メタ）アクリル酸
およびそのエステルの重合防止方法。1. As a polymerization inhibitor of (meth) acrylic acid and its ester, 2,2,6,6-tetramethylpiperidinooxyl, 4-hydroxy-2,2,6,6-tetramethylpiperidi Nooxyl and 4,4 ', 4 "-tris- (2,2,6,6
-Using one or more N-oxyl compounds selected from the group consisting of tetramethylpiperidinooxyl) phosphite, one or more phenol compounds selected from the group consisting of hydroquinone and metoquinone, and a phenothiazine compound. A method for preventing polymerization of (meth) acrylic acid and its ester, which comprises:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7100894A JP2725593B2 (en) | 1993-04-15 | 1994-04-08 | Method for preventing polymerization of (meth) acrylic acid and its ester |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8890893 | 1993-04-15 | ||
| JP5-88908 | 1993-04-15 | ||
| JP7100894A JP2725593B2 (en) | 1993-04-15 | 1994-04-08 | Method for preventing polymerization of (meth) acrylic acid and its ester |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06345681A true JPH06345681A (en) | 1994-12-20 |
| JP2725593B2 JP2725593B2 (en) | 1998-03-11 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7100894A Expired - Fee Related JP2725593B2 (en) | 1993-04-15 | 1994-04-08 | Method for preventing polymerization of (meth) acrylic acid and its ester |
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| JP (1) | JP2725593B2 (en) |
Cited By (29)
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| JPH0753449A (en) * | 1993-08-09 | 1995-02-28 | Mitsubishi Chem Corp | Method for preventing polymerization of (meth)acrylic acid or (meth)acrylic acid ester |
| JPH0967311A (en) * | 1995-08-31 | 1997-03-11 | Nippon Shokubai Co Ltd | Prevention of polymerization of acrylic esters |
| JPH09143380A (en) * | 1995-08-29 | 1997-06-03 | Basf Ag | Filling composition for chemical hardening fixation |
| JPH10226682A (en) * | 1997-02-18 | 1998-08-25 | Mitsubishi Gas Chem Co Inc | Production of cyclic formal |
| WO1999024402A1 (en) * | 1997-11-12 | 1999-05-20 | Mitsubishi Rayon Co., Ltd. | N-oxyl compounds, process for the preparation thereof, and process for inhibiting the polymerization of vinyl monomers with the same |
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| JP2000103763A (en) * | 1998-07-27 | 2000-04-11 | Nippon Shokubai Co Ltd | Prevention of polymerization of vinyl compound |
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| JP2001302678A (en) * | 2000-04-21 | 2001-10-31 | Chisso Corp | Method for producing purified acryloxy group-or methacryloxy group-containing organosilicon compound |
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| JP2002155021A (en) * | 2000-11-16 | 2002-05-28 | Toagosei Co Ltd | Polymerization inhibitor composition for vinyl monomer and method for producing high-purity (meth)acrylic acid |
| JP2002275126A (en) * | 2001-01-10 | 2002-09-25 | Nippon Shokubai Co Ltd | Method for producing hydroxyalkyl (meth)acrylate |
| JP2002539104A (en) * | 1999-03-06 | 2002-11-19 | ビーエーエスエフ アクチェンゲゼルシャフト | Acrylic acid production method |
| JP2003119205A (en) * | 2001-10-12 | 2003-04-23 | Asahi Denka Kogyo Kk | Polymerization inhibitor composition |
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| US6888026B2 (en) | 2001-09-28 | 2005-05-03 | Nippon Shokubai Co., Ltd. | Method for producing (meth)acrylic acid |
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| JP2005272382A (en) * | 2004-03-25 | 2005-10-06 | Hakuto Co Ltd | Method for inhibiting polymerization of (meth)acrylic acid and (meth)acrylic ester |
| US7005544B2 (en) | 2002-09-03 | 2006-02-28 | Nippon Shokubai Co., Ltd. | Method for preventing polymerization in an acrylic acid manufacturing process |
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| KR100885077B1 (en) * | 2007-04-24 | 2009-02-25 | 전병준 | Method of anti-polymerization in the methyl metacrylate monomer process |
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| JP2015509513A (en) * | 2012-03-05 | 2015-03-30 | エボニック レーム ゲゼルシャフト ミット ベシュレンクテル ハフツングＥｖｏｎｉｋ Ｒｏｅｈｍ ＧｍｂＨ | Stabilized (meth) acrylic monomer |
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| JP2017502001A (en) * | 2013-12-26 | 2017-01-19 | ダウ グローバル テクノロジーズ エルエルシー | Combination of inhibitors for lithium salt-catalyzed transesterification process and method for removing lithium salt |
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|---|---|---|---|---|
| JPH0753449A (en) * | 1993-08-09 | 1995-02-28 | Mitsubishi Chem Corp | Method for preventing polymerization of (meth)acrylic acid or (meth)acrylic acid ester |
| JPH09143380A (en) * | 1995-08-29 | 1997-06-03 | Basf Ag | Filling composition for chemical hardening fixation |
| JPH0967311A (en) * | 1995-08-31 | 1997-03-11 | Nippon Shokubai Co Ltd | Prevention of polymerization of acrylic esters |
| JP2001505601A (en) * | 1996-11-27 | 2001-04-24 | ビーエーエスエフ アクチェンゲゼルシャフト | Polymerization method of vinyl monomer |
| JPH10226682A (en) * | 1997-02-18 | 1998-08-25 | Mitsubishi Gas Chem Co Inc | Production of cyclic formal |
| WO1999024402A1 (en) * | 1997-11-12 | 1999-05-20 | Mitsubishi Rayon Co., Ltd. | N-oxyl compounds, process for the preparation thereof, and process for inhibiting the polymerization of vinyl monomers with the same |
| JPH11302223A (en) * | 1998-04-27 | 1999-11-02 | Asahi Chem Ind Co Ltd | Production of cyclohexyl methacrylate |
| JP2000103763A (en) * | 1998-07-27 | 2000-04-11 | Nippon Shokubai Co Ltd | Prevention of polymerization of vinyl compound |
| JP2000119352A (en) * | 1998-10-14 | 2000-04-25 | Nippon Shokubai Co Ltd | Resin composition |
| JP2002539104A (en) * | 1999-03-06 | 2002-11-19 | ビーエーエスエフ アクチェンゲゼルシャフト | Acrylic acid production method |
| JP4673483B2 (en) * | 1999-03-06 | 2011-04-20 | ビーエーエスエフ ソシエタス・ヨーロピア | Acrylic acid production method |
| JP2003515575A (en) * | 1999-12-02 | 2003-05-07 | クロムプトン コーポレイション | Inhibition of polymerization of unsaturated monomers |
| JP2001328960A (en) * | 2000-03-13 | 2001-11-27 | Nippon Shokubai Co Ltd | Method for producing hydroxyalkyl (meth)acrylate |
| JP2001302678A (en) * | 2000-04-21 | 2001-10-31 | Chisso Corp | Method for producing purified acryloxy group-or methacryloxy group-containing organosilicon compound |
| JP2002155021A (en) * | 2000-11-16 | 2002-05-28 | Toagosei Co Ltd | Polymerization inhibitor composition for vinyl monomer and method for producing high-purity (meth)acrylic acid |
| JP2002275126A (en) * | 2001-01-10 | 2002-09-25 | Nippon Shokubai Co Ltd | Method for producing hydroxyalkyl (meth)acrylate |
| US6888026B2 (en) | 2001-09-28 | 2005-05-03 | Nippon Shokubai Co., Ltd. | Method for producing (meth)acrylic acid |
| JP2003119205A (en) * | 2001-10-12 | 2003-04-23 | Asahi Denka Kogyo Kk | Polymerization inhibitor composition |
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| US7005544B2 (en) | 2002-09-03 | 2006-02-28 | Nippon Shokubai Co., Ltd. | Method for preventing polymerization in an acrylic acid manufacturing process |
| JP4548821B2 (en) * | 2004-03-25 | 2010-09-22 | 伯東株式会社 | Method for inhibiting polymerization of (meth) acrylic acid and (meth) acrylic acid ester |
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| KR101538836B1 (en) * | 2010-06-18 | 2015-07-22 | 하쿠토 가부시키가이샤 | Polymerization inhibitor composition for vinyl compounds and method for inhibiting the polymerization of vinyl compounds which includes using same |
| JP2015509513A (en) * | 2012-03-05 | 2015-03-30 | エボニック レーム ゲゼルシャフト ミット ベシュレンクテル ハフツングＥｖｏｎｉｋ Ｒｏｅｈｍ ＧｍｂＨ | Stabilized (meth) acrylic monomer |
| JP2017502001A (en) * | 2013-12-26 | 2017-01-19 | ダウ グローバル テクノロジーズ エルエルシー | Combination of inhibitors for lithium salt-catalyzed transesterification process and method for removing lithium salt |
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