JPH09316026A - Prevention of polymerization of (meth)acrylic acid and its ester - Google Patents
Prevention of polymerization of (meth)acrylic acid and its esterInfo
- Publication number
- JPH09316026A JPH09316026A JP13176696A JP13176696A JPH09316026A JP H09316026 A JPH09316026 A JP H09316026A JP 13176696 A JP13176696 A JP 13176696A JP 13176696 A JP13176696 A JP 13176696A JP H09316026 A JPH09316026 A JP H09316026A
- Authority
- JP
- Japan
- Prior art keywords
- acrylic acid
- polymerization
- meth
- oxyl
- formula
- 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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- Hydrogenated Pyridines (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、（メタ）アクリル
酸及びそのエステルの重合防止方法に関する。詳しく
は、本発明は、Ｎ−オキシル化合物及び特定のリン化合
物を併用することにより（メタ）アクリル酸及びそのエ
ステルの重合を防止する方法に関する。TECHNICAL FIELD The present invention relates to a method for preventing polymerization of (meth) acrylic acid and its ester. Specifically, the present invention relates to a method for preventing the polymerization of (meth) acrylic acid and its ester by using an N-oxyl compound and a specific phosphorus compound in combination.
【０００２】[0002]
【従来の技術】（メタ）アクリル酸及びそのエステルは
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）アクリル酸及びそのエ
ステルについては、保存中の重合を防止するため種々の
重合防止剤が単独或いは数種組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 ester have a property of being easily spontaneously polymerized by light or heat. Therefore, for (meth) acrylic acid and its ester, various polymerization inhibitors are added to the monomer individually or in combination of several kinds in order to prevent polymerization during storage.
【０００３】一方、気相接触反応により（メタ）アクリ
ル酸を製造する際の蒸留工程においては、（メタ）アク
リル酸の水溶液を共沸分離塔で蒸留するため共存する
水、酢酸、アルデヒド類のために（メタ）アクリル酸の
重合が極めて起こり易くなっており、蒸留中にポリマー
が生成して蒸留塔の運転ができなくなるというトラブル
が発生する。そして、この場合、保存中のモノマーの重
合を防止する重合防止剤を通常の量使用しても重合を防
止することができず、このため、（メタ）アクリル酸の
製造工程における重合防止方法についても従来からいろ
いろ提案されている。On the other hand, in the distillation step in the production of (meth) acrylic acid by a gas phase catalytic reaction, an aqueous solution of (meth) acrylic acid is distilled in an azeotropic separation column so that coexisting water, acetic acid, and aldehydes are removed. Therefore, the polymerization of (meth) acrylic acid is extremely likely to occur, and a problem occurs that a polymer is generated during distillation and the distillation column cannot be operated. In this case, the polymerization cannot be prevented even by using a usual amount of a polymerization inhibitor for preventing the polymerization of the monomer during storage, and therefore, the method for preventing polymerization in the production process of (meth) acrylic acid Has been proposed in the past.
【０００４】例えば、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−オキシル又は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提案されてい
る。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
提案されている。更に、特開平６−３４５６８１号公報
には、アクリル酸及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−テトラメチルピペリジン−
１−オキシル類、ハイドロキノン類及びフェノチアジン
の併用を、また、特開平８−４８６５０号公報には、
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−オキシル化合物と、マンガ
ン塩化合物、銅塩化合物、２，２，６，６−テトラメチ
ルピペリジン化合物及びニトロソ化合物等との併用によ
る重合防止方法について提案がある。For example, in Japanese Patent Publication No. 54-3853, as a polymerization inhibitor in the production of methacrylic acid from methacrolein using an oxygen-containing gas in an organic solvent,
A method using 2,2,6,6-tetramethyl-4-hydroxypiperidine-1-oxyl or 2,2,6,6-tetramethylpiperidine-1-oxyl has been proposed. Moreover, Japanese Patent Publication No. 58-46496 discloses 2,2.
A method using a compound such as 5,5-tetramethyl-3-oxopyrrolidine-1-oxyl or 2,2,6,6-tetramethyl-4-acetoxypiperidine-1-oxyl has been proposed. Further, in JP-A-6-345681, 2,2,6,6-tetramethylpiperidine-is disclosed as a method for preventing the polymerization of acrylic acid and acrylic acid esters.
The combined use of 1-oxyls, hydroquinones and phenothiazine, and JP-A-8-48650,
N-oxyl compounds such as 2,2,6,6-tetramethyl-4-hydroxypiperidine-1-oxyl, manganese salt compounds, copper salt compounds, 2,2,6,6-tetramethylpiperidine compounds and nitroso compounds There is a proposal for a method of preventing polymerization by using the above together with the like.
【０００５】[0005]
【発明が解決しようとする課題】しかしながら、本発明
者等が、上記先行技術について追試を行ったところ、こ
れらの方法ではモノマーの蒸留工程における重合を完全
に抑制することはできないことが判明した。本発明の課
題は、（メタ）アクリル酸及びそのエステルについて従
来技術より優れた重合防止方法を提供することにある。However, when the present inventors made additional tests on the above-mentioned prior art, it was found that these methods cannot completely suppress the polymerization in the distillation step of the monomer. An object of the present invention is to provide a method for preventing polymerization of (meth) acrylic acid and its ester, which is superior to the prior art.
【０００６】[0006]
【課題を解決するための手段】本発明者等は上記課題を
解決すべく鋭意検討を行った結果、これまで報告の無い
Ｎ−オキシル化合物とリン化合物の併用により、（メ
タ）アクリル酸及び（メタ）アクリル酸エステルの重合
抑制効果が発現されることを見出し本発明を完成するに
至った。Means for Solving the Problems As a result of intensive investigations to solve the above problems, the present inventors have found that (meth) acrylic acid and (( The inventors have found that the effect of suppressing the polymerization of (meth) acrylic acid ester is exhibited, and have completed the present invention.
【０００７】即ち、本発明は、重合防止剤としては、Ｎ
−オキシル化合物及びリン化合物を併用することを特徴
とする（メタ）アクリル酸及びそのエステルの重合防止
方法、にある。以下、本発明の方法について詳細に説明
する。That is, in the present invention, N is used as the polymerization inhibitor.
-A method for preventing polymerization of (meth) acrylic acid and its ester, characterized in that an oxyl compound and a phosphorus compound are used in combination. Hereinafter, the method of the present invention will be described in detail.
【０００８】[0008]
（１）Ｎ−オキシル化合物 本発明に用いられるＮ−オキシル化合物として好ましい
ものは、式（Ｉ）(1) N-oxyl compound Preferred as the N-oxyl compound used in the present invention is the compound of formula (I)
【０００９】[0009]
【化５】 （式中、Ａは、ＣＨ2 、ＣＨＯＨ、Ｃ＝Ｏ、ＣＨＯＣＯ
ＣＨ3 又はＣＨＮＨＣＯＣＨ3 を示す）で表わされる
２，２，６，６−テトラメチルピペリジン−１−オキシ
ル類である。Embedded image (In the formula, A is CH 2 , CHOH, C═O, CHOCO
2,3,6,6-tetramethylpiperidine-1-oxyl represented by CH 3 or CHNHCOCH 3 .
【００１０】式（Ｉ）の化合物の具体例としては、２，
２，６，６−テトラメチルピペリジン−１−オキシル、
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、２，２，６，６−テトラメチル−
４−オキソピペリジン−１−オキシル、２，２，６，６
−テトラメチル−４−アセチルピペリジン−１−オキシ
ル、２，２，６，６−テトラメチル−４−アセトアミド
ピペリジン−１−オキシル等が挙げられる。この中、
２，２，６，６−テトラメチルピペリジン−１−オキシ
ル、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、２，２，６，６−テトラメチ
ル−４−オキソピペリジン−１−オキシルが好ましい。
これらの化合物は単独でも、或いは二種以上組合わせて
使用することもできる。Ｎ−オキシル化合物の添加量
は、（メタ）アクリル酸及び（メタ）アクリル酸エステ
ルに対して、通常、５〜１０００重量ｐｐｍ、好ましく
は、５０〜５００ｐｐｍの範囲より選ばれる。Specific examples of the compound of formula (I) include 2,
2,6,6-tetramethylpiperidine-1-oxyl,
2,2,6,6-tetramethyl-4-hydroxypiperidine-1-oxyl, 2,2,6,6-tetramethyl-
4-oxopiperidine-1-oxyl, 2,2,6,6
-Tetramethyl-4-acetylpiperidine-1-oxyl, 2,2,6,6-tetramethyl-4-acetamidopiperidine-1-oxyl and the like can be mentioned. In this
2,2,6,6-tetramethylpiperidine-1-oxyl, 2,2,6,6-tetramethyl-4-hydroxypiperidine-1-oxyl, 2,2,6,6-tetramethyl-4-oxo Piperidine-1-oxyl is preferred.
These compounds may be used alone or in combination of two or more. The amount of the N-oxyl compound added is usually 5 to 1000 ppm by weight, preferably 50 to 500 ppm, relative to (meth) acrylic acid and (meth) acrylic acid ester.
【００１１】（２）リン化合物 本発明に用いられるリン化合物として好ましいものは、
式（II）で表わされる化合物である。(2) Phosphorus Compound Preferred as the phosphorus compound used in the present invention are:
It is a compound represented by the formula (II).
【００１２】[0012]
【化６】 （式中、Ｒ、Ｒ′及びＲ″は、炭素数１〜１０のアルキ
ル基、アリール基又は炭素数１〜６のアルキル基を有す
るアルコキシ基を示し、それぞれ同一でも異なってもよ
い）[Chemical 6] (In the formula, R, R ′, and R ″ represent an alkyl group having 1 to 10 carbon atoms, an aryl group, or an alkoxy group having an alkyl group having 1 to 6 carbon atoms, which may be the same or different)
【００１３】式（II）の化合物の具体例としては、式
（III)のホスフィン化合物と式（IV）の亜リン酸エステ
ルが挙げられる。Specific examples of the compound of the formula (II) include a phosphine compound of the formula (III) and a phosphorous acid ester of the formula (IV).
【００１４】[0014]
【化７】 （式中、Ｒ1 、Ｒ2 及びＲ3 は、炭素数１〜１０のアル
キル基又はアリール基を示し、それぞれ同一でも異なっ
てもよい）[Chemical 7] (In the formula, R 1 , R 2 and R 3 represent an alkyl group or an aryl group having 1 to 10 carbon atoms and may be the same or different)
【００１５】[0015]
【化８】 （式中、Ｒ4 、Ｒ5 及びＲ6 は、炭素数１〜６のアルキ
ル基を示し、それぞれ同一でも異なってもよい）Embedded image (In the formula, R 4 , R 5 and R 6 represent an alkyl group having 1 to 6 carbon atoms and may be the same or different)
【００１６】式（III)のホスフィン化合物の具体例とし
ては、トリメチルホスフィン、トリエチルホスフィン、
トリ−ｎ−プロピルホスフィン、トリ−ｉ−プロピルホ
スフィン、トリ−ｎ−ブチルホスフィン、トリ−ｉ−ブ
チルホスフィン、トリフェニルホスフィン、ジメチルフ
ェニルホスフィン、メチルジフェニルホスフィン等が挙
げられる。この中、トリフェニルホスフィン、トリ−ｎ
−ブチルホスフィンが好ましい。Specific examples of the phosphine compound of the formula (III) include trimethylphosphine, triethylphosphine,
Examples thereof include tri-n-propylphosphine, tri-i-propylphosphine, tri-n-butylphosphine, tri-i-butylphosphine, triphenylphosphine, dimethylphenylphosphine, and methyldiphenylphosphine. Among these, triphenylphosphine and tri-n
-Butylphosphine is preferred.
【００１７】また、式（IV）の亜リン酸エステルの具体
例としては、亜リン酸トリメチル、亜リン酸トリエチ
ル、亜リン酸トリ−ｎ−プロピル、亜リン酸トリ−ｉ−
プロピル、亜リン酸トリ−ｎ−ブチル、亜リン酸トリ−
ｉ−ブチル、亜リン酸トリヘキシル等が挙げられる。こ
の中、亜リン酸トリエチルが好ましい。Specific examples of the phosphite of the formula (IV) include trimethyl phosphite, triethyl phosphite, tri-n-propyl phosphite, and tri-i-phosphite.
Propyl, tri-n-butyl phosphite, tri-phosphite
Examples thereof include i-butyl and trihexyl phosphite. Of these, triethyl phosphite is preferred.
【００１８】これらのリン化合物は、単独でも、或いは
混合して使用することもできる。リン化合物の添加量
は、（メタ）アクリル酸及び（メタ）アクリル酸エステ
ルに対して、通常、１０〜５０００重量ｐｐｍ、好まし
くは、５０〜１０００ｐｐｍの範囲より選ばれる。本発
明の重合禁止剤組成物は従来公知の重合禁止剤、例え
ば、ハイドロキノン、メトキシキノン、ジフェニルアミ
ン、フェニレンジアミン等と組合わせて使用することも
できる。しかし、フェノチアジン、酢酸銅、ジアルキル
ジチオカルバミン酸銅塩、２，２，６，６−テトラメチ
ル−４−ヒドロキシ−ピペリジン等とは、特に、Ｎ−オ
キシル化合物との相性が悪く、重合を促進する傾向にあ
るので好ましくない。These phosphorus compounds may be used alone or as a mixture. The addition amount of the phosphorus compound is usually 10 to 5000 ppm by weight, preferably 50 to 1000 ppm, relative to (meth) acrylic acid and (meth) acrylic acid ester. The polymerization inhibitor composition of the present invention can also be used in combination with conventionally known polymerization inhibitors such as hydroquinone, methoxyquinone, diphenylamine, phenylenediamine and the like. However, phenothiazine, copper acetate, dialkyldithiocarbamic acid copper salt, 2,2,6,6-tetramethyl-4-hydroxy-piperidine, etc. are particularly poor in compatibility with N-oxyl compounds and tend to promote polymerization. It is not preferable because it is in.
【００１９】（３）重合防止方法 本発明の重合防止方法は、ビニル化合物の中でも特に重
合し易い（メタ）アクリル酸及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。(3) Polymerization Inhibition Method The polymerization inhibition method of the present invention can be preferably used for (meth) acrylic acid and its ester which are particularly easily polymerized among vinyl compounds. Examples of the acrylate ester include methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, and the like. , Methyl methacrylate, butyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate and the like can be mentioned as applicable objects.
【００２０】重合防止方法としては、例えば気相接触酸
化反応により（メタ）アクリル酸を製造する場合につい
て説明すると、（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、前記重合防止剤を（メタ）アク
リル酸と共存させればよい。As a method for preventing polymerization, for example, a case of producing (meth) acrylic acid by a gas phase catalytic oxidation reaction will be described. A (meth) acrylic acid rectification column, (meth)
In various distillation steps such as a separation column of acrylic acid and solvent, a separation tower of (meth) acrylic acid and light boiling components such as acetic acid, etc. The polymerization inhibitor may coexist with (meth) acrylic acid.
【００２１】本発明の重合防止方法は、前記二成分の重
合防止剤を前記諸工程において添加すればよく、添加方
法については特に限定されない。即ち、固体又は粉体等
の形で直接添加してもよいし、或いは他の有機溶媒の溶
液として添加してもよい。また、添加時期についても特
に制限はなく、各成分を個別に、或いは同時に、例えば
一つの溶液の形で添加してもよい。また、本発明の重合
禁止剤組成物は分子状酸素と併用することにより、重合
禁止効果が更に向上し、製造装置の長期運転が可能とな
る。分子状酸素としては、酸素ガスそのものでもよい
し、窒素等の不活性ガスに希釈したものを用いてもよい
が、経済的には空気を用いる方法が好ましい。分子状酸
素の供給方法については、エア−バブリング等により
（メタ）アクリル酸及び（メタ）アクリル酸エステルに
直接混入させてもよいし、或いは他の溶媒に溶解した状
態で間接的に供給してもよい。蒸留塔やストリッパーの
塔底、或いはリボイラーからガス状で供給するとエアー
バブリングを簡単に製造工程に組み込むことができる。
分子状酸素は、（メタ）アクリル酸及び（メタ）アクリ
ル酸エステルの蒸留蒸気量に対して０．０５〜１容量％
程度供給するのが望ましい。In the method for preventing polymerization of the present invention, the two-component polymerization inhibitor may be added in the various steps, and the addition method is not particularly limited. That is, it may be added directly in the form of solid or powder, or may be added as a solution of another organic solvent. The timing of addition is also not particularly limited, and each component may be added individually or simultaneously, for example, in the form of one solution. When the polymerization inhibitor composition of the present invention is used in combination with molecular oxygen, the polymerization inhibition effect is further improved and the production apparatus can be operated for a long period of time. As the molecular oxygen, oxygen gas itself may be used, or one diluted with an inert gas such as nitrogen may be used, but the method using air is economically preferable. Regarding the method of supplying the molecular oxygen, it may be directly mixed with the (meth) acrylic acid and the (meth) acrylic acid ester by air bubbling or the like, or may be indirectly supplied in a state of being dissolved in another solvent. Good. Air bubbling can be easily incorporated into the manufacturing process by supplying it in a gaseous state from the bottom of a distillation column or stripper, or from a reboiler.
Molecular oxygen is 0.05 to 1% by volume with respect to the distillation vapor amount of (meth) acrylic acid and (meth) acrylic acid ester.
It is desirable to supply a degree.
【００２２】[0022]
【実施例】以下、実施例及び比較例を挙げて本発明を更
に具体的に説明するが、本発明はその要旨を越えない限
り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 and comparative examples, but the present invention is not limited to the examples as long as the gist thereof is not exceeded.
【００２３】実施例１ 塔底部が５００ｍＬガラス製フラスコで、塔頂部に留出
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、プロピレンの気相接触酸化反応によって得られた粗
製アクリル酸を水で吸収した組成をモデル的に調製した
ものを用いた。即ち、アクリル酸５１．５重量％、酢酸
＝２．５重量％、水＝４６．０重量％とし、更に、２，
２，６，６−テトラメチルピペリジン−１−オキシル及
びトリフェニルホスフィンをそれぞれアクリル酸に対し
１５０ｐｐｍ及び３００ｐｐｍ添加した。この原料液を
蒸留塔へ２７０ｍＬ／時の量を供給した。また、共沸剤
としてトルエンを用いて還流液として循環させながら蒸
留を行った。操作条件は、塔底温度＝９０℃、塔頂温度
＝５０℃、塔頂圧力＝１８０Ｔｏｒｒで行った。また、
空気を塔底部よりキャピラリー管より３００Ｎ−ｍＬ／
時（０．１５容量％）の量で供給した。定常状態での塔
底抜き出し液の組成は、アクリル酸＝８９．７重量％、
酢酸＝３．７重量％、水＝０．３重量％、トルエン＝
６．３重量％であった。８時間の運転時間において塔内
でポリマーは全く発生しなかった。Example 1 Aqueous acrylic acid solution was subjected to azeotropic separation using a packed column having a 500 mL glass flask at the bottom, a distillation tube at the top of the tower, and a raw material supply tube at the center. As a feedstock, a composition prepared by modeling a crude acrylic acid obtained by a vapor phase catalytic oxidation reaction of propylene and absorbing it with water was used. That is, acrylic acid 51.5% by weight, acetic acid = 2.5% by weight, water = 46.0% by weight, and
150 ppm and 300 ppm of 2,6,6-tetramethylpiperidine-1-oxyl and triphenylphosphine were added to acrylic acid, respectively. This raw material liquid was supplied to the distillation column in an amount of 270 mL / hour. Distillation was performed while using toluene as an azeotropic agent and circulating it as a reflux liquid. Operating conditions were column bottom temperature = 90 ° C., column top temperature = 50 ° C., column top pressure = 180 Torr. Also,
Air from the bottom of the tower to 300 N-mL /
Hourly (0.15% by volume). In the steady state, the composition of the column bottom withdrawal liquid is acrylic acid = 89.7% by weight,
Acetic acid = 3.7% by weight, water = 0.3% by weight, toluene =
It was 6.3% by weight. At an operating time of 8 hours, no polymer was generated in the tower.
【００２４】実施例２ 実施例１の方法において、重合禁止剤として、２，２，
６，６−テトラメチル−４−ヒドロキシピペリジン−１
−オキシル及びトリフェニルホスフィンをそれぞれ２０
０ｐｐｍ及び３００ｐｐｍ添加した以外は同様に行った
結果、塔底フラスコ部に僅かにポリマーらしきものが生
成した以外は全くポリマーの生成は認められなかった。Example 2 In the method of Example 1, as the polymerization inhibitor, 2,2
6,6-Tetramethyl-4-hydroxypiperidine-1
-Oxyl and triphenylphosphine each 20
As a result of performing the same except that 0 ppm and 300 ppm were added, no polymer was observed except that a little polymer-like thing was generated in the bottom flask part.
【００２５】実施例３ 実施例１の方法において、重合禁止剤として、２，２，
６，６−テトラメチルピペリジン−１−オキシル及び亜
リン酸トリエチルをそれぞれ１５０ｐｐｍ及び３００ｐ
ｐｍ添加した以外は同様に行った結果、ポリマーの生成
は全く認められなかった。Example 3 In the method of Example 1, as the polymerization inhibitor, 2,2
6,6-Tetramethylpiperidine-1-oxyl and triethyl phosphite were added at 150 ppm and 300 p, respectively.
As a result of performing the same procedure except that pm was added, no polymer formation was observed.
【００２６】実施例４ 実施例１の方法において、重合禁止剤として、２，２，
６，６−テトラメチルピペリジン−１−オキシル、トリ
フェニルホスフィン、及び、ハイドロキノンをそれぞれ
１００ｐｐｍ、３００ｐｐｍ、及び８００ｐｐｍ用いた
以外は同様に行った結果、ポリマーの生成は全く認めら
れなかった。Example 4 In the method of Example 1, as the polymerization inhibitor, 2,2
As a result of the same procedure except that 6,6-tetramethylpiperidine-1-oxyl, triphenylphosphine, and hydroquinone were used at 100 ppm, 300 ppm, and 800 ppm, respectively, no polymer formation was observed.
【００２７】比較例１ 実施例１の方法において、重合禁止剤として２，２，
６，６−テトラメチルピペリジン−１−オキシルのみを
１５０ｐｐｍ用いた以外は同様に行った結果、充填剤か
らフラスコの首部にかけて少量のポリマーの生成が認め
られた。Comparative Example 1 In the method of Example 1, 2,2 as the polymerization inhibitor
As a result of performing the same operation except that only 6,6-tetramethylpiperidine-1-oxyl was used at 150 ppm, a small amount of polymer was observed from the filler to the neck of the flask.
【００２８】比較例２ 実施例１の方法において、重合禁止剤としてトリフェニ
ルホスフィンのみを３００ｐｐｍ用いた以外は同様に行
った結果、充填剤からフラスコの首部にかけて相当量の
ポリマーの生成が認められた。Comparative Example 2 The same procedure as in Example 1 was carried out except that only 300 ppm of triphenylphosphine was used as the polymerization inhibitor, and as a result, a considerable amount of polymer was observed from the filler to the neck of the flask. .
【００２９】[0029]
【発明の効果】本発明によれば、重合防止剤としてＮ−
オキシル化合物とリン化合物とを併用することにより
（メタ）アクリル酸及びそのエステルの製造工程におけ
る重合をほぼ完全に抑制することができる。According to the present invention, N- as a polymerization inhibitor is used.
By using the oxyl compound and the phosphorus compound in combination, the polymerization of (meth) acrylic acid and its ester in the production process can be almost completely suppressed.
Claims (5)
及びリン化合物を併用することを特徴とする（メタ）ア
クリル酸及びそのエステルの重合防止方法。1. A method for preventing polymerization of (meth) acrylic acid and its ester, which comprises using an N-oxyl compound and a phosphorus compound together as a polymerization inhibitor.
（Ｉ） 【化１】 （式中、Ａは、ＣＨ2 、ＣＨＯＨ、Ｃ＝Ｏ、ＣＨＯＣＯ
ＣＨ3 又はＣＨＮＨＣＯＣＨ3 を示す）で表わされる
２，２，６，６−テトラメチルピペリジン−１−オキシ
ル類を用いる請求項１に記載の方法。2. An N-oxyl compound represented by the general formula (I): (In the formula, A is CH 2 , CHOH, C═O, CHOCO
The method according to claim 1, wherein 2,2,6,6-tetramethylpiperidine-1-oxyl represented by CH 3 or CHNHCOCH 3 ) is used.
ル基、アリール基又は炭素数１〜６のアルキル基を有す
るアルコキシ基を示し、それぞれ同一でも異なってもよ
い）で表わされる化合物を用いる請求項１又は２に記載
の方法。3. A phosphorus compound having the general formula (II): (In the formula, R, R ′, and R ″ represent an alkyl group having 1 to 10 carbon atoms, an aryl group, or an alkoxy group having an alkyl group having 1 to 6 carbon atoms, which may be the same or different) The method according to claim 1 or 2, wherein the compound is used.
（III) 【化３】 （式中、Ｒ1 、Ｒ2 及びＲ3 は、炭素数１〜１０のアル
キル基又はアリール基を示し、それぞれ同一でも異なっ
てもよい）で表わされるホスフィン化合物を用いる請求
項１ないし３のいずれか１項に記載の方法。4. The phosphorus compound of formula (II) has the general formula (III): A phosphine compound represented by the formula (wherein R 1 , R 2 and R 3 represent an alkyl group or an aryl group having 1 to 10 carbon atoms and may be the same or different). The method according to item 1.
（IV） 【化４】 （式中、Ｒ4 、Ｒ5 及びＲ6 は、炭素数１〜６のアルキ
ル基を示し、それぞれ同一でも異なってもよい）で表わ
される亜リン酸エステルを用いる請求項１ないし３のい
ずれか１項に記載の方法。5. The phosphorus compound of the formula (II) is represented by the general formula (IV): A phosphite represented by the formula (wherein R 4 , R 5 and R 6 represent an alkyl group having 1 to 6 carbon atoms and may be the same or different). The method according to item 1.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13176696A JPH09316026A (en) | 1996-05-27 | 1996-05-27 | Prevention of polymerization of (meth)acrylic acid and its ester |
| US08/863,192 US5856562A (en) | 1996-05-27 | 1997-05-27 | Method for inhibiting polymerization of (meth) acrylic acid or esters thereof |
| DE69701590T DE69701590T2 (en) | 1996-05-27 | 1997-05-27 | Process for inhibiting the polymerization of (meth) acrylic acid and its esters |
| EP97303569A EP0810196B1 (en) | 1996-05-27 | 1997-05-27 | Method for inhibiting polymerization of (meth) acrylic acid or esters thereof |
| CZ19971622A CZ290225B6 (en) | 1996-05-27 | 1997-05-27 | Method for inhibiting the polymerization of (meth)acrylic acid and esters thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13176696A JPH09316026A (en) | 1996-05-27 | 1996-05-27 | Prevention of polymerization of (meth)acrylic acid and its ester |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH09316026A true JPH09316026A (en) | 1997-12-09 |
Family
ID=15065673
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP13176696A Withdrawn JPH09316026A (en) | 1996-05-27 | 1996-05-27 | Prevention of polymerization of (meth)acrylic acid and its ester |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH09316026A (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0801092A2 (en) * | 1996-04-09 | 1997-10-15 | Basf Aktiengesellschaft | Stabilised aqueous dispersions of polymers having ethylenic unsaturated groups |
| WO1999044972A1 (en) * | 1998-03-03 | 1999-09-10 | Nippon Zeon Co., Ltd. | Polymerization-inhibiting composition, polymerization inhibitor and method for inhibiting polymerization |
| JP2000103763A (en) * | 1998-07-27 | 2000-04-11 | Nippon Shokubai Co Ltd | Prevention of polymerization of vinyl compound |
| JP2000169429A (en) * | 1998-12-10 | 2000-06-20 | Mitsubishi Rayon Co Ltd | Production of high-purity (meth)acrylic ester |
| JP2001302678A (en) * | 2000-04-21 | 2001-10-31 | Chisso Corp | Method for producing purified acryloxy or methacryloxy group-containing organosilicon compound |
| JP2005272382A (en) * | 2004-03-25 | 2005-10-06 | Hakuto Co Ltd | Method for inhibiting polymerization of (meth) acrylic acid and (meth) acrylic acid ester |
| US7288169B2 (en) | 2001-08-22 | 2007-10-30 | Mitsubishi Chemical Corporation | Distillation apparatus for readily polymerizable compound |
| JP2009249308A (en) * | 2008-04-03 | 2009-10-29 | Seiko Kagaku Kk | Discoloration preventive agent |
| JP4556227B2 (en) * | 1999-02-05 | 2010-10-06 | 日本曹達株式会社 | Stabilizer and stabilization method for acid chloride |
-
1996
- 1996-05-27 JP JP13176696A patent/JPH09316026A/en not_active Withdrawn
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0801092A3 (en) * | 1996-04-09 | 1999-03-17 | Basf Aktiengesellschaft | Stabilised aqueous dispersions of polymers having ethylenic unsaturated groups |
| EP0801092A2 (en) * | 1996-04-09 | 1997-10-15 | Basf Aktiengesellschaft | Stabilised aqueous dispersions of polymers having ethylenic unsaturated groups |
| US6770222B1 (en) | 1998-03-03 | 2004-08-03 | Nippon Zeon Co., Ltd. | Polymerization-inhibiting composition, polymerization inhibitor and method for inhibiting polymerization |
| WO1999044972A1 (en) * | 1998-03-03 | 1999-09-10 | Nippon Zeon Co., Ltd. | Polymerization-inhibiting composition, polymerization inhibitor and method for inhibiting polymerization |
| JP2000103763A (en) * | 1998-07-27 | 2000-04-11 | Nippon Shokubai Co Ltd | Prevention of polymerization of vinyl compound |
| JP2000169429A (en) * | 1998-12-10 | 2000-06-20 | Mitsubishi Rayon Co Ltd | Production of high-purity (meth)acrylic ester |
| JP4556227B2 (en) * | 1999-02-05 | 2010-10-06 | 日本曹達株式会社 | Stabilizer and stabilization method for acid chloride |
| JP2001302678A (en) * | 2000-04-21 | 2001-10-31 | Chisso Corp | Method for producing purified acryloxy or methacryloxy group-containing organosilicon compound |
| US7288169B2 (en) | 2001-08-22 | 2007-10-30 | Mitsubishi Chemical Corporation | Distillation apparatus for readily polymerizable compound |
| US7473338B2 (en) | 2001-08-22 | 2009-01-06 | Mitsubishi Chemical Corporation | Distillation apparatus for readily polymerizable compound |
| JP2005272382A (en) * | 2004-03-25 | 2005-10-06 | Hakuto Co Ltd | Method for inhibiting polymerization of (meth) acrylic acid and (meth) acrylic acid ester |
| 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 |
| JP2009249308A (en) * | 2008-04-03 | 2009-10-29 | Seiko Kagaku Kk | Discoloration preventive agent |
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