JP2008174494A - Methylenemalonic acid composition and method for stabilizing the same - Google Patents
Methylenemalonic acid composition and method for stabilizing the same Download PDFInfo
- Publication number
- JP2008174494A JP2008174494A JP2007009789A JP2007009789A JP2008174494A JP 2008174494 A JP2008174494 A JP 2008174494A JP 2007009789 A JP2007009789 A JP 2007009789A JP 2007009789 A JP2007009789 A JP 2007009789A JP 2008174494 A JP2008174494 A JP 2008174494A
- Authority
- JP
- Japan
- Prior art keywords
- acid compound
- malonic acid
- composition
- methylene malonic
- acid
- 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.)
- Pending
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
本発明は、保存安定性に優れたメチレンマロン酸組成物、およびメチレンマロン酸組成物の安定化方法に関するものである。 The present invention relates to a methylene malonic acid composition having excellent storage stability and a method for stabilizing a methylene malonic acid composition.
メチレンマロン酸のホモポリマーは、比較的低温度（２３５℃）でメチレンマロン酸に分解することから、プリント配線板等製造時のバインダーとしての利用が期待されている。
しかし、メチレンマロン酸は、活性なビニル基を有している単量体であるため、熱に対して不安定で、室温以上に加熱すると該メチレンマロン酸化合物のオリゴマーを生成し、さらに加熱を続けると無色透明のガラス状の高分子量化合物（重合物）となる。特に、高純度のメチレンマロン酸化合物は、室温での貯蔵時においても、重合反応を起こして高沸点の不純物を生成する欠点があった。このような問題を解消するために、酢酸銅等を安定化剤として添加する方法やハイドロキノン等の重合禁止剤を安定化剤として添加する方法が開示されている。（非特許文献１）
However, since methylene malonic acid is a monomer having an active vinyl group, it is unstable to heat, and when heated to room temperature or higher, an oligomer of the methylene malonic acid compound is formed and further heated. If it continues, it will become a colorless and transparent glassy high molecular weight compound (polymer). In particular, the high-purity methylene malonic acid compound has a drawback in that it generates a high-boiling impurity by causing a polymerization reaction even during storage at room temperature. In order to solve such problems, a method of adding copper acetate or the like as a stabilizer and a method of adding a polymerization inhibitor such as hydroquinone as a stabilizer are disclosed. (Non-Patent Document 1)
しかしながら、上記の安定化剤では、重合抑制の効果が充分に発揮されず、ハイドロキノン等の安定剤を多量に添加すると経時変化によって化合物に着色がおこるため、メチレンマロン酸を安定化することには改善の余地があった。
そこで、本発明で解決しようとする課題は、反応性を損なうことなく、長期に保存しても安定性が良く、着色の少ないメチレンマロン酸組成物を提供すること、さらに、メチレンマロン酸組成物の安定化方法を提供することにある。
However, with the above-mentioned stabilizer, the effect of inhibiting polymerization is not sufficiently exhibited, and when a stabilizer such as hydroquinone is added in a large amount, the compound is colored due to aging, so that methylenemalonic acid is stabilized. There was room for improvement.
Accordingly, the problem to be solved by the present invention is to provide a methylene malonic acid composition that has good stability even when stored for a long period of time without impairing reactivity, and has little coloration. Further, the methylene malonic acid composition It is to provide a stabilization method.
上記諸目的は、一般式（１） The above objects are obtained by the general formula (1)
（式中、Ｒ1、R2は水素原子またはアルキル基を表す）で示されるメチレンマロン酸化合物と、酸化防止剤と、酸とを共存させることを特徴とする安定化方法によって達成される。
本発明はまた、前記の酸をメチレンマロン酸組成物中に１０ｐｐｍ以上の割合で共存させることを特徴とするメチレンマロン酸化合物の安定化方法を示すものである。
本発明はさらに、上記一般式（１）で示されるメチレンマロン酸化合物と、酸化防止剤と、酸とを含有してなるメチレンマロン酸化合物組成物を示すものである。
(In the formula, R 1 and R 2 represent a hydrogen atom or an alkyl group). This is achieved by a stabilization method characterized by coexisting an antioxidant and an acid.
The present invention also shows a method for stabilizing a methylene malonic acid compound, characterized in that the above-mentioned acid is allowed to coexist in a methylene malonic acid composition at a ratio of 10 ppm or more.
The present invention further shows a methylene malonic acid compound composition comprising the methylene malonic acid compound represented by the general formula (1), an antioxidant, and an acid.
本発明によれば、メチレンマロン酸化合物の反応性を損なうことなく、例えば、製造時、貯蔵時または輸送時等において、メチレンマロン酸化合物の重合や着色等による変質を防止することができ、長期にわたって安定性を向上させることができるという効果を奏する。 According to the present invention, without impairing the reactivity of the methylenemalonic acid compound, for example, during production, storage or transportation, it is possible to prevent alteration due to polymerization or coloring of the methylenemalonic acid compound, and for a long time. There is an effect that the stability can be improved.
以下に本発明を詳しく説明する。本発明における前記一般式（１）で示されるメチレンマロン酸、つまり、安定化されるべきメチレンマロン酸化合物は、例えば、一般式（２） The present invention is described in detail below. The methylene malonic acid represented by the general formula (1) in the present invention, that is, the methylene malonic acid compound to be stabilized is, for example, the general formula (2)
（式中、Ｒ1、R2は水素原子またはアルキル基を表す）で示されるマロン酸化合物と、アルデヒド系化合物とを反応させることにより容易に得られる。尚、メチレンマロン酸化合物は非特許文献１に開示の製造方法等により得られるが、特に限定されるものではない。 It is easily obtained by reacting a malonic acid compound represented by the formula (wherein R 1 and R 2 represent a hydrogen atom or an alkyl group) and an aldehyde compound. The methylene malonic acid compound can be obtained by the production method disclosed in Non-Patent Document 1, but is not particularly limited.
上記Ｒ1 、Ｒ2 で示される置換基は、それぞれ独立して水素原子または炭素数１〜１８の直鎖状または枝分かれ鎖状のアルキル基を表す。
上記のマロン酸化合物としては、具体的には、（ａ）Ｒ1、R2で示される置換基が水素原子であるマロン酸、（ｂ）Ｒ1、R2で示される置換基が炭素数１〜１８のアルキル基であるマロン酸アルキル、例えばマロン酸メチル、マロン酸エチル、マロン酸−ｎ−プロピル、マロン酸イソプロピル、マロン酸−ｎ−ブチル、マロン酸イソブチル、マロン酸−ｔ−ブチル、マロン酸−ｎ−オクチル、マロン酸イソオクチル、マロン酸−２−エチルヘキシル、マロン酸ラウリル、マロン酸ステアリル等が挙げられる。
これらマロン酸エステルのうち、マロン酸メチル、マロン酸エチル、マロン酸−ｎ−ブチル、マロン酸−２−エチルヘキシルが特に好適である。
The substituents represented by R 1 and R 2 each independently represent a hydrogen atom or a linear or branched alkyl group having 1 to 18 carbon atoms.
Specific examples of the malonic acid compound include (a) malonic acid in which the substituents represented by R 1 and R 2 are hydrogen atoms, and (b) the substituent represented by R 1 and R 2 has a carbon number. Alkyl malonate which is an alkyl group of 1 to 18 such as methyl malonate, ethyl malonate, n-propyl malonate, isopropyl malonate, n-butyl malonate, isobutyl malonate, t-butyl malonate, Examples include malonate-n-octyl, isooctyl malonate, 2-ethylhexyl malonate, lauryl malonate, stearyl malonate, and the like.
Of these malonic acid esters, methyl malonate, ethyl malonate, n-butyl malonate, and 2-ethylhexyl malonate are particularly suitable.
上記 アルデヒド系化合物としては、具体的には、例えば、ホルムアルデヒド、ホルムアルデヒドの重合体（２量体〜１００量体）であるパラホルムアルデヒド等が挙げられる。
上記のマロン酸化合物およびアルデヒド系化合物を反応させることにより、相当するメチレンマロン酸化合物、つまり、本発明にかかる上記一般式（１）で示されるメチレンマロン酸化合物が得られる。即ち、上記一般式（１）で示されるメチレンマロン酸化合物は、式中、Ｒ1、R2で示される置換基が水素原子またはアルキル基である化合物である。上記Ｒで示される置換基とは、具体的には、水素原子、炭素数１〜１８のアルキル基を示す。
Specific examples of the aldehyde-based compound include formaldehyde and paraformaldehyde which is a polymer of formaldehyde (dimer to 100-mer).
By reacting the malonic acid compound and the aldehyde compound, the corresponding methylenemalonic acid compound, that is, the methylenemalonic acid compound represented by the general formula (1) according to the present invention is obtained. That is, the methylene malonic acid compound represented by the general formula (1) is a compound in which the substituents represented by R 1 and R 2 are hydrogen atoms or alkyl groups. Specifically, the substituent represented by R represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms.
本発明にかかる安定化方法に用いられる酸化防止剤としては、具体的には、例えば、ｐ−メトキシフェノール、２，６−ジ−ｔ−ブチル−４−メチルフェノール、２，６−ジ−ｔ−ブチル−４−エチルフェノール、２，４−ジ−ｔ−ブチルフェノール、２，４，６−トリ−ｔ−ブチルフェノール、２，２'−メチレンビス−（４−メチル−６−ｔ−ブチルフェノール）、２，２'−メチレンビス−（４−エチル−６−ｔ−ブチルフェノール）、４，４'−ブチリデンビス−（３−メチル−６−ｔ−ブチルフェノール）、４，４'−チオビス−（３−メチル−６−ｔ−ブチルフェノール）、ｎ−オクタデシル・３−（４−ヒドロキシ−３，５−ジ−ｔ−ブチルフェニル）プロピオネート、３，３−ビス−（３−ｔ−ブチル−４−ヒドロキシフェニル）エチレンエステル、テトラキス〔メチレン−３−（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオネート〕メタン、トリエチレングリコール−ビス−〔３−（３−ｔ−ブチル−５−メチル−４−ヒドロキシフェニル）プロピオネート〕、ペンタエリスリチル−テトラキス〔３−（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオネート〕、１，６−ヘキサンジオール−ビス−〔３−（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオネート〕、１，１，３−トリス（２−メチル−４−ヒドロキシ−５−ｔ−ブチルフェニル）ブタン、１，１，３−トリス（４−ヒドロキシ−５−ｔ−ブチルフェニル）ブタン、１，１，３−トリス（２−エチル−４−ヒドロキシ−５−ｔ−ブチルフェニル）ブタン、１，１，３−トリス（２−プロピル−４−ヒドロキシ−５−ｔ−ブチルフェニル）ブタン、１，１，３−トリス（２，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）ブタン、１，１，３−トリス（２，６−ジメチル−４−ヒドロキシ−５−ｔ−ブチルフェニル）ブタン、１，１，３−トリス（２，５，６−トリ−ｔ−ブチル−４−ヒドロキシフェニル）ブタン、１，１，３−トリス（２−メチル−４−ヒドロキシ−５−ｔ−アミルフェニル）ブタン、１，１，３−トリス（４−ヒドロキシ−５−ｔ−アミルフェニル）ブタン、１，１，３−トリス（２−エチル−４−ヒドロキシ−５−ｔ−アミルフェニル）ブタン、１，１，３−トリス（２−プロピル−４−ヒドロキシ−５−ｔ−アミルフェニル）ブタン、１，１，３−トリス（２，５−ジ−ｔ−アミル−４−ヒドロキシフェニル）ブタン、１，１，３−トリス（２，６−ジメチル−４−ヒドロキシ−５−ｔ−アミルフェニル）ブタン、１，１，３−トリス（２，５，６−トリ−ｔ−アミル−４−ヒドロキシフェニル）ブタン等の置換フェノール等が挙げられるが、これら例示の化合物に限定されるものではない。 Specific examples of the antioxidant used in the stabilization method according to the present invention include p-methoxyphenol, 2,6-di-t-butyl-4-methylphenol, and 2,6-di-t. -Butyl-4-ethylphenol, 2,4-di-t-butylphenol, 2,4,6-tri-t-butylphenol, 2,2'-methylenebis- (4-methyl-6-t-butylphenol), 2 , 2′-methylenebis- (4-ethyl-6-tert-butylphenol), 4,4′-butylidenebis- (3-methyl-6-tert-butylphenol), 4,4′-thiobis- (3-methyl-6) -T-butylphenol), n-octadecyl 3- (4-hydroxy-3,5-di-t-butylphenyl) propionate, 3,3-bis- (3-t-butyl-4-hydroxyphenyl) Ethylene ester, tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane, triethylene glycol-bis- [3- (3-t-butyl-5-methyl-4) -Hydroxyphenyl) propionate], pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis- [3- (3,5 -Di-t-butyl-4-hydroxyphenyl) propionate], 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,1,3-tris (4- Hydroxy-5-t-butylphenyl) butane, 1,1,3-tris (2-ethyl-4-hydroxy-5-t-butylphenyl) butane, 1,3-tris (2-propyl-4-hydroxy-5-tert-butylphenyl) butane, 1,1,3-tris (2,5-di-tert-butyl-4-hydroxyphenyl) butane, 1,3-tris (2,6-dimethyl-4-hydroxy-5-t-butylphenyl) butane, 1,1,3-tris (2,5,6-tri-t-butyl-4-hydroxyphenyl) Butane, 1,1,3-tris (2-methyl-4-hydroxy-5-t-amylphenyl) butane, 1,1,3-tris (4-hydroxy-5-t-amylphenyl) butane, 1,3-tris (2-ethyl-4-hydroxy-5-t-amylphenyl) butane, 1,1,3-tris (2-propyl-4-hydroxy-5-t-amylphenyl) butane, 1,3-tris (2,5-di- -Amyl-4-hydroxyphenyl) butane, 1,1,3-tris (2,6-dimethyl-4-hydroxy-5-t-amylphenyl) butane, 1,1,3-tris (2,5,6 Substituted phenols such as -tri-t-amyl-4-hydroxyphenyl) butane and the like can be mentioned, but are not limited to these exemplified compounds.
これら酸化防止剤は、単独で用いてもよく、また、二種類以上を適宜混合して用いてもよい。これら例示の化合物のうち、ｐ−メトキシフェノール、２，６−ジ−ｔ−ブチル−４−メチルフェノール、および１，１，３−トリス（２−メチル−４−ヒドロキシ−５−ｔ−ブチルフェニル）ブタン（以下、AO30と記す）が特に好ましい。 These antioxidants may be used alone or in combination of two or more. Of these exemplary compounds, p-methoxyphenol, 2,6-di-t-butyl-4-methylphenol, and 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) ) Butane (hereinafter referred to as AO30) is particularly preferred.
メチレンマロン酸化合物に対する酸化防止剤の添加量は、メチレンマロン酸化合物の種類、用いる酸化防止剤の種類、併用する酸の使用量等に応じて、最適な量となるように、適宜設定すればよい。具体的には、例えば、メチレンマロン酸化合物に対して、酸化防止剤を、１０ｐｐｍ〜１００００ｐｐｍの範囲内、より好ましくは５０ｐｐｍ〜５０００ｐｐｍの範囲内で、特に好ましくは１００ｐｐｍ〜２０００ｐｐｍの範囲内で添加すればよい。これにより、酸化防止剤の性能を充分に発揮させることができるので、メチレンマロン酸化合物の安定性を向上させることができる。酸化防止剤の添加量が１０ｐｐｍよりも少ない場合には、不純物、特にオリゴマーの生成を充分に抑制することができないおそれがある。また、酸化防止剤の添加量を１００００ｐｐｍよりも多くしても、不純物の生成を抑制する効果のさらなる改善は望めず、添加した酸化防止剤の一部が無駄になり、経済的に不利となるおそれがある。 The amount of the antioxidant added to the methylene malonic acid compound can be appropriately set so as to be an optimum amount depending on the type of methylene malonic acid compound, the type of antioxidant used, the amount of acid used in combination, etc. Good. Specifically, for example, an antioxidant is added within a range of 10 ppm to 10000 ppm, more preferably within a range of 50 ppm to 5000 ppm, and particularly preferably within a range of 100 ppm to 2000 ppm with respect to the methylene malonic acid compound. That's fine. Thereby, since the performance of the antioxidant can be sufficiently exhibited, the stability of the methylenemalonic acid compound can be improved. When the addition amount of the antioxidant is less than 10 ppm, there is a possibility that the generation of impurities, particularly oligomers, cannot be sufficiently suppressed. Further, even if the addition amount of the antioxidant is more than 10000 ppm, further improvement of the effect of suppressing the generation of impurities cannot be expected, and a part of the added antioxidant is wasted, which is economically disadvantageous. There is a fear.
本発明にかかる安定化方法に用いられる酸としては、具体的には、例えば、（メタ）アクリル酸、蟻酸、酢酸、酪酸、フェノール、置換フェノール等の一塩基酸、フタル酸、テレフタル酸、コハク酸、マレイン酸等の二塩基酸、トリメリット酸、ピロメリット酸、ブタンテトラカルボン酸等の多塩基酸等が挙げられるが、これら例示の化合物に限定されるものではない。これら酸は、単独で用いてもよく、二種類以上を適宜混合して用いてもよい。 Specific examples of the acid used in the stabilization method of the present invention include, for example, (meth) acrylic acid, formic acid, acetic acid, butyric acid, phenol, monobasic acids such as substituted phenol, phthalic acid, terephthalic acid, and succinic acid. Examples thereof include dibasic acids such as acid and maleic acid, and polybasic acids such as trimellitic acid, pyromellitic acid, and butanetetracarboxylic acid, but are not limited to these exemplified compounds. These acids may be used alone or in combination of two or more.
メチレンマロン酸化合物に対する酸の使用量は、特に限定されるものではなく、メチレンマロン酸化合物の種類、用いる酸の種類、併用する酸化防止剤の添加量等に応じて、最適な量となるように適宜設定すればよい。具体的には、例えば、メチレンマロン酸化合物に対して、酸を１０ｐｐｍ以上、好ましくは１００ｐｐｍ〜５０質量％、より好ましくは１０００ｐｐｍ〜４５質量％の範囲内で、さらに好ましくは１質量％〜４０質量％、特に好ましくは１０質量％〜３５質量％の範囲内で添加すればよい。これにより、メチレンマロン酸化合物の安定性をより一層向上させることができる。酸の添加量が１０ｐｐｍ未満の場合には、不純物の生成を充分に抑制することができず、例えば室温付近での貯蔵時において品質の低下が生じる等、メチレンマロン酸化合物の安定性を充分に向上させることができないおそれがある。 The amount of acid used with respect to the methylene malonic acid compound is not particularly limited, and may be an optimal amount depending on the type of methylene malonic acid compound, the type of acid used, the amount of antioxidant used in combination, and the like. May be set as appropriate. Specifically, for example, the acid is 10 ppm or more, preferably 100 ppm to 50% by mass, more preferably 1000 ppm to 45% by mass, and further preferably 1% to 40% by mass with respect to the methylenemalonic acid compound. %, Particularly preferably within a range of 10% by mass to 35% by mass. Thereby, the stability of the methylenemalonic acid compound can be further improved. When the amount of acid added is less than 10 ppm, the generation of impurities cannot be sufficiently suppressed, and the stability of the methylene malonic acid compound is sufficiently improved, for example, the quality deteriorates during storage near room temperature. There is a possibility that it cannot be improved.
上記のメチレンマロン酸化合物と酸化防止剤および酸とを共存させることにより、本発明にかかる組成物、即ち、メチレンマロン酸化合物を含む組成物が得られる。
本発明のメチレンマロン酸化合物と酸化防止剤と酸とを共存させる方法は、特に限定されるものではない。例えば、高純度のメチレンマロン酸化合物に酸化防止剤と酸とを、上記例示の添加量となるように添加してもよい。また、粗製のメチレンマロン酸化合物に所定量の酸化防止剤と酸とを添加した後、例えば製品化する際に蒸留等の精製工程を行って、メチレンマロン酸化合物に対する酸化防止剤の添加量と酸の添加量とを調整してもよい。
By allowing the methylenemalonic acid compound to coexist with an antioxidant and an acid, the composition according to the present invention, that is, the composition containing the methylenemalonic acid compound can be obtained.
The method for allowing the methylenemalonic acid compound of the present invention, the antioxidant and the acid to coexist is not particularly limited. For example, an antioxidant and an acid may be added to a high-purity methylene malonic acid compound so as to have the above-described exemplary addition amounts. In addition, after adding a predetermined amount of an antioxidant and an acid to the crude methylene malonic acid compound, a purification step such as distillation is performed when the product is commercialized, for example, and the addition amount of the antioxidant to the methylene malonic acid compound You may adjust the addition amount of an acid.
本発明のメチレンマロン酸化合物と酸化防止剤と酸とを共存させる際においては、これら化合物を取り扱う雰囲気中の酸素濃度を１容量％〜３０容量％の範囲内、より好ましくは５容量％〜２５容量％の範囲内に調節すればよい。これにより、メチレンマロン酸化合物の安定性をさらに一層向上させることができる。尚、上記化合物の取り扱いは、例えば、窒素やアルゴン等の不活性ガスと酸素とからなる混合ガスの気流下で行えばよいが、特に限定されるものではない。 When the methylene malonic acid compound of the present invention, an antioxidant and an acid coexist, the oxygen concentration in the atmosphere in which these compounds are handled is in the range of 1% by volume to 30% by volume, more preferably 5% by volume to 25%. What is necessary is just to adjust within the range of volume%. Thereby, the stability of the methylene malonic acid compound can be further improved. In addition, although the handling of the said compound may be performed under the airflow of the mixed gas which consists of inert gas, such as nitrogen and argon, and oxygen, for example, it is not specifically limited.
本発明のメチレンマロン酸化合物を含む組成物を取り扱う際には、該組成物が封入等される容器の気相部の酸素濃度を、上記例示の範囲内に調節すればよい。これにより、メチレンマロン酸化合物の安定性をさらに一層向上させることができる。尚、気相部の酸素濃度を調節する方法としては、例えば、窒素やアルゴン等の不活性ガスを容器の気相部に導入する方法、不活性ガスと酸素とからなる混合ガスを用いて気相部を置換する方法等が挙げられるが、特に限定されるものではない。 When the composition containing the methylene malonic acid compound of the present invention is handled, the oxygen concentration in the gas phase part of the container in which the composition is enclosed may be adjusted within the above-illustrated range. Thereby, the stability of the methylene malonic acid compound can be further improved. As a method for adjusting the oxygen concentration in the gas phase portion, for example, a method of introducing an inert gas such as nitrogen or argon into the gas phase portion of the container, a gas mixture using an inert gas and oxygen is used. Although the method etc. which substitute a phase part are mentioned, it does not specifically limit.
本発明のメチレンマロン酸化合物を含む組成物を取り扱う際には、気温が４０℃以下、より好ましくは３０℃以下に調節すればよい。 When handling the composition containing the methylene malonic acid compound of the present invention, the temperature may be adjusted to 40 ° C. or lower, more preferably 30 ° C. or lower.
本発明にかかるメチレンマロン酸化合物の安定化方法は、以上のように、前記一般式（１）で示されるメチレンマロン酸化合物と酸化防止剤と酸とを共存させる方法である。
上記の方法によれば、メチレンマロン酸化合物の反応性を損なうことなく、例えば貯蔵時や輸送時、製造時等における該メチレンマロン酸化合物の変質を防止することができ、メチレンマロン酸化合物の安定性を向上させることができる。また、上記の安定化方法は、メチレンマロン酸化合物の反応性に対して悪影響を及ぼさないので、例えば使用時にメチレンマロン酸化合物を精製する必要が無く、工業的に価値が高い。
As described above, the method for stabilizing a methylene malonic acid compound according to the present invention is a method in which a methylene malonic acid compound represented by the general formula (1), an antioxidant, and an acid coexist.
According to the above method, without deteriorating the reactivity of the methylene malonic acid compound, for example, it is possible to prevent alteration of the methylene malonic acid compound during storage, transportation, production, etc. Can be improved. In addition, the above stabilization method does not adversely affect the reactivity of the methylenemalonic acid compound, so that it is not necessary to purify the methylenemalonic acid compound at the time of use, for example, and is industrially valuable.
また、本発明にかかるメチレンマロン酸化合物を含む組成物は、以上のように、前記一般式（１）で示されるメチレンマロン酸化合物と、酸化防止剤と、酸とを含む構成である。この構成によれば、上記の組成物はメチレンマロン酸化合物の誘導体または重合体を製造する際に、該メチレンマロン酸化合物の副反応を抑制することができる。即ち、上記の組成物は、メチレンマロン酸化合物の反応性に対して悪影響を及ぼさないので、例えば使用時にメチレンマロン酸化合物を精製する必要が無く、工業的に価値が高い。 Moreover, the composition containing the methylenemalonic acid compound concerning this invention is a structure containing the methylenemalonic acid compound shown by the said General formula (1), antioxidant, and an acid as mentioned above. According to this configuration, the above composition can suppress a side reaction of the methylene malonic acid compound when producing the derivative or polymer of the methylene malonic acid compound. That is, since the above composition does not adversely affect the reactivity of the methylenemalonic acid compound, for example, it is not necessary to purify the methylenemalonic acid compound at the time of use, and is industrially valuable.
以下、実施例および比較例により、本発明をさらに具体的に説明するが、本発明はこれらにより何ら限定されるものではない。
〔実施例１〕
密栓することができる内容積１０ｍｌのガラス瓶に、蒸留によって精製したメチレンマロン酸化合物としてのメチレンマロン酸ジメチル（以下、ＭＭＤＭと記す）５ｇを入れた。次に、このＭＭＤＭに、酸化防止剤としてのＡＯ３０をＭＭＤＭに対して２０００ｐｐｍとなるように添加すると共に、酢酸をＭＭＤＭに対して１２質量％となるように添加して組成物とした。また、ガラス瓶の気相部の酸素濃度を２１容量％に調節した。組成物の外観性状は無色透明液であった。上記添加量をまとめて表１に記載した。
そして、上記の組成物が入ったガラス瓶を密栓（密閉）した後、該ガラス瓶を、温度５℃で静置して、ＭＭＤＭの経時変化、つまり、安定性を評価した。即ち、５℃で静置してからの組成物の外観性状を目視にて確認すると共に、該組成物を１Ｈ−ＮＭＲを用いて分析し、オリゴマー並びに高分子量化合物（重合物）の生成の有無を確認した。
結果を表２に記載した。
EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further more concretely, this invention is not limited at all by these.
[Example 1]
5 g of dimethyl methylenemalonate (hereinafter referred to as MMDM) as a methylenemalonic acid compound purified by distillation was put into a glass bottle having an internal volume of 10 ml that can be sealed. Next, AO30 as an antioxidant was added to this MMDM so that it might become 2000 ppm with respect to MMDM, and acetic acid was added so that it might become 12 mass% with respect to MMDM, and it was set as the composition. The oxygen concentration in the gas phase part of the glass bottle was adjusted to 21% by volume. The appearance of the composition was a colorless transparent liquid. The above addition amounts are summarized in Table 1.
And after sealing (sealing) the glass bottle containing said composition, this glass bottle was left still at the temperature of 5 degreeC, and the time-dependent change of MMDM, ie, stability, was evaluated. That is, the appearance of the composition after standing at 5 ° C. is confirmed visually, and the composition is analyzed using 1H-NMR to determine whether oligomers and high molecular weight compounds (polymers) are formed. It was confirmed.
The results are shown in Table 2.
〔実施例２〕
ＡＯ３０とｐ−メトキシフェノールをＭＭＤＭに対して各１０００ｐｐｍとなるように添加した以外は、実施例１と同様の操作を行い、組成物とした。上記添加量をまとめて表１に記載した。次に、この組成物を用いて実施例１と同様の操作を行い、ＭＭＤＭの安定性を評価した。結果を表２に記載した。
[Example 2]
The same operation as in Example 1 was carried out except that AO30 and p-methoxyphenol were added to each 1000 ppm with respect to MMDM to obtain a composition. The above addition amounts are summarized in Table 1. Next, the same operation as in Example 1 was performed using this composition, and the stability of MMDM was evaluated. The results are shown in Table 2.
〔実施例３〕ＡＯ３０とハイドロキノンをＭＭＤＭに対して各１０００ｐｐｍとなるように添加した以外は、実施例１と同様の操作を行い、組成物とした。上記添加量をまとめて表１に記載した。次に、この組成物を用いて実施例１と同様の操作を行い、ＭＭＤＭの安定性を評価した。結果を表２に記載した。 [Example 3] A composition was prepared in the same manner as in Example 1 except that AO30 and hydroquinone were added at 1000 ppm each with respect to MMDM. The above addition amounts are summarized in Table 1. Next, the same operation as in Example 1 was performed using this composition, and the stability of MMDM was evaluated. The results are shown in Table 2.
〔実施例４〕
ＡＯ３０をＭＭＤＭに対して１０００ｐｐｍとなるように添加した以外は、実施例１と同様の操作を行い、組成物とした。上記添加量をまとめて表１に記載した。次に、この組成物を用いて実施例１と同様の操作を行い、ＭＭＤＭの安定性を評価した。結果を表２に記載した。
Example 4
A composition was obtained by performing the same operation as in Example 1 except that AO30 was added to 1000 ppm with respect to MMDM. The above addition amounts are summarized in Table 1. Next, the same operation as in Example 1 was performed using this composition, and the stability of MMDM was evaluated. The results are shown in Table 2.
〔実施例５〕
実施例４における酢酸の添加量をＭＭＤＭに対して１６質量％となるように添加した以外は、実施例４と同様の操作を行い、組成物とした。上記添加量をまとめて表１に記載した。次に、この組成物を用いて実施例４と同様の操作を行い、ＭＭＤＭの安定性を評価した。結果を表２に記載した。
Example 5
A composition was obtained by performing the same operation as in Example 4, except that the amount of acetic acid added in Example 4 was 16% by mass with respect to MMDM. The above addition amounts are summarized in Table 1. Next, this composition was used in the same manner as in Example 4 to evaluate the stability of MMDM. The results are shown in Table 2.
〔実施例６〕
実施例４における酢酸の添加量をＭＭＤＭに対して３３質量％となるように添加した以外は、実施例４と同様の操作を行い、組成物とした。上記添加量をまとめて表１に記載した。次に、この組成物を用いて実施例４と同様の操作を行い、ＭＭＤＭの安定性を評価した。結果を表２に記載した。
Example 6
A composition was obtained in the same manner as in Example 4 except that the amount of acetic acid added in Example 4 was 33% by mass with respect to MMDM. The above addition amounts are summarized in Table 1. Next, this composition was used in the same manner as in Example 4 to evaluate the stability of MMDM. The results are shown in Table 2.
〔比較例１〕
実施例４における酢酸の添加量をＭＭＤＭに対して８質量％となるように水酸化カリウムで中和した以外は、実施例４と同様の操作を行い、比較用の組成物とした。次に、この組成物を用いて実施例１と同様の操作を行い、ＭＭＤＭの安定性を評価した。結果を表２に記載した。尚、中和が起こると同時に重合し、非常に不安定であった。
[Comparative Example 1]
A comparative composition was prepared by performing the same operation as in Example 4 except that the amount of acetic acid added in Example 4 was neutralized with potassium hydroxide so as to be 8% by mass with respect to MMDM. Next, the same operation as in Example 1 was performed using this composition, and the stability of MMDM was evaluated. The results are shown in Table 2. The polymerization occurred at the same time as the neutralization occurred, and it was very unstable.
比較例１については酢酸を水酸化カリウムで中和。 For Comparative Example 1, acetic acid was neutralized with potassium hydroxide.
表２に記載した結果から明らかなように、本実施例にかかる組成物は、比較例１〜２の比較用組成物と比べて、重合物の生成が抑制されることが判った。また、ヒドロキノンに代えてＡＯ３０やｐ−メトキシフェノールを用いるとＭＭＤＭの安定性が向上する事が判った。 As is clear from the results described in Table 2, it was found that the composition according to the present example suppresses the formation of a polymer compared to the comparative compositions of Comparative Examples 1 and 2. It was also found that the stability of MMDM was improved when AO30 or p-methoxyphenol was used instead of hydroquinone.
Claims (3)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007009789A JP2008174494A (en) | 2007-01-19 | 2007-01-19 | Methylenemalonic acid composition and method for stabilizing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007009789A JP2008174494A (en) | 2007-01-19 | 2007-01-19 | Methylenemalonic acid composition and method for stabilizing the same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2008174494A true JP2008174494A (en) | 2008-07-31 |
Family
ID=39701785
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2007009789A Pending JP2008174494A (en) | 2007-01-19 | 2007-01-19 | Methylenemalonic acid composition and method for stabilizing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2008174494A (en) |
Cited By (25)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2427422A1 (en) * | 2009-05-07 | 2012-03-14 | Optmed Inc. | Improved methylidene malonate process |
| US8975435B2 (en) | 2009-05-07 | 2015-03-10 | Optmed, Inc. | Methylidene malonate process |
| US9181365B2 (en) | 2012-03-30 | 2015-11-10 | Sirrus, Inc. | Methods for activating polymerizable compositions, polymerizable systems, and products formed thereby |
| US9217098B1 (en) | 2015-06-01 | 2015-12-22 | Sirrus, Inc. | Electroinitiated polymerization of compositions having a 1,1-disubstituted alkene compound |
| US9234107B2 (en) | 2012-03-30 | 2016-01-12 | Sirrus, Inc. | Ink coating formulations and polymerizable systems for producing the same |
| US9249265B1 (en) | 2014-09-08 | 2016-02-02 | Sirrus, Inc. | Emulsion polymers including one or more 1,1-disubstituted alkene compounds, emulsion methods, and polymer compositions |
| US9279022B1 (en) | 2014-09-08 | 2016-03-08 | Sirrus, Inc. | Solution polymers including one or more 1,1-disubstituted alkene compounds, solution polymerization methods, and polymer compositions |
| US9315597B2 (en) | 2014-09-08 | 2016-04-19 | Sirrus, Inc. | Compositions containing 1,1-disubstituted alkene compounds for preparing polymers having enhanced glass transition temperatures |
| US9334430B1 (en) | 2015-05-29 | 2016-05-10 | Sirrus, Inc. | Encapsulated polymerization initiators, polymerization systems and methods using the same |
| US9416091B1 (en) | 2015-02-04 | 2016-08-16 | Sirrus, Inc. | Catalytic transesterification of ester compounds with groups reactive under transesterification conditions |
| CN105949358A (en) * | 2010-10-20 | 2016-09-21 | 瑟拉斯公司 | Synthesis of methylene malonates substantially free of impurities |
| US9512058B2 (en) | 2011-10-19 | 2016-12-06 | Sirrus Inc. | Multifunctional monomers, methods for making multifunctional monomers, polymerizable compostions and products formed thereform |
| US9518001B1 (en) | 2016-05-13 | 2016-12-13 | Sirrus, Inc. | High purity 1,1-dicarbonyl substituted-1-alkenes and methods for their preparation |
| US9522381B2 (en) | 2013-01-11 | 2016-12-20 | Sirrus, Inc. | Method to obtain methylene malonate via bis(hydroxymethyl) malonate pathway |
| US9567475B1 (en) | 2016-06-03 | 2017-02-14 | Sirrus, Inc. | Coatings containing polyester macromers containing 1,1-dicarbonyl-substituted 1 alkenes |
| US9617377B1 (en) | 2016-06-03 | 2017-04-11 | Sirrus, Inc. | Polyester macromers containing 1,1-dicarbonyl-substituted 1 alkenes |
| US9752059B2 (en) | 2012-11-16 | 2017-09-05 | Sirrus, Inc. | Plastics bonding systems and methods |
| US9828324B2 (en) | 2010-10-20 | 2017-11-28 | Sirrus, Inc. | Methylene beta-diketone monomers, methods for making methylene beta-diketone monomers, polymerizable compositions and products formed therefrom |
| US10047192B2 (en) | 2012-06-01 | 2018-08-14 | Sirrus, Inc. | Optical material and articles formed therefrom |
| US10196481B2 (en) | 2016-06-03 | 2019-02-05 | Sirrus, Inc. | Polymer and other compounds functionalized with terminal 1,1-disubstituted alkene monomer(s) and methods thereof |
| US10414839B2 (en) | 2010-10-20 | 2019-09-17 | Sirrus, Inc. | Polymers including a methylene beta-ketoester and products formed therefrom |
| US10428177B2 (en) | 2016-06-03 | 2019-10-01 | Sirrus, Inc. | Water absorbing or water soluble polymers, intermediate compounds, and methods thereof |
| US10501400B2 (en) | 2015-02-04 | 2019-12-10 | Sirrus, Inc. | Heterogeneous catalytic transesterification of ester compounds with groups reactive under transesterification conditions |
| US10607910B2 (en) | 2012-11-30 | 2020-03-31 | Sirrus, Inc. | Composite compositions for electronics applications |
| US10913875B2 (en) | 2012-03-30 | 2021-02-09 | Sirrus, Inc. | Composite and laminate articles and polymerizable systems for producing the same |
-
2007
- 2007-01-19 JP JP2007009789A patent/JP2008174494A/en active Pending
Cited By (54)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9487468B2 (en) | 2009-05-07 | 2016-11-08 | Optmed, Inc. | Methylidene malonate process |
| EP2427422A4 (en) * | 2009-05-07 | 2013-01-16 | Optmed Inc | Improved methylidene malonate process |
| US8975435B2 (en) | 2009-05-07 | 2015-03-10 | Optmed, Inc. | Methylidene malonate process |
| US8993795B2 (en) | 2009-05-07 | 2015-03-31 | Optmed Inc | Methylidene malonate process |
| US9540309B2 (en) | 2009-05-07 | 2017-01-10 | Optmed, Inc. | Methylidene malonate process |
| EP2427423A1 (en) * | 2009-05-07 | 2012-03-14 | Optmed Inc. | Improved methylidene malonate process |
| EP2427422A1 (en) * | 2009-05-07 | 2012-03-14 | Optmed Inc. | Improved methylidene malonate process |
| EP2427423A4 (en) * | 2009-05-07 | 2013-01-16 | Optmed Inc | Improved methylidene malonate process |
| US9828324B2 (en) | 2010-10-20 | 2017-11-28 | Sirrus, Inc. | Methylene beta-diketone monomers, methods for making methylene beta-diketone monomers, polymerizable compositions and products formed therefrom |
| US10414839B2 (en) | 2010-10-20 | 2019-09-17 | Sirrus, Inc. | Polymers including a methylene beta-ketoester and products formed therefrom |
| CN105949358A (en) * | 2010-10-20 | 2016-09-21 | 瑟拉斯公司 | Synthesis of methylene malonates substantially free of impurities |
| US9512058B2 (en) | 2011-10-19 | 2016-12-06 | Sirrus Inc. | Multifunctional monomers, methods for making multifunctional monomers, polymerizable compostions and products formed thereform |
| US9969822B2 (en) | 2011-10-19 | 2018-05-15 | Sirrus, Inc. | Multifunctional monomers, methods for making multifunctional monomers, polymerizable compositions and products formed therefrom |
| US9527795B2 (en) | 2011-10-19 | 2016-12-27 | Sirrus, Inc. | Methylene beta-ketoester monomers, methods for making methylene beta-ketoester monomers, polymerizable compositions and products formed therefrom |
| US9234107B2 (en) | 2012-03-30 | 2016-01-12 | Sirrus, Inc. | Ink coating formulations and polymerizable systems for producing the same |
| US10913875B2 (en) | 2012-03-30 | 2021-02-09 | Sirrus, Inc. | Composite and laminate articles and polymerizable systems for producing the same |
| US9523008B2 (en) | 2012-03-30 | 2016-12-20 | Sirrus, Inc. | Ink coating formulations and polymerizable systems for producing the same |
| US9181365B2 (en) | 2012-03-30 | 2015-11-10 | Sirrus, Inc. | Methods for activating polymerizable compositions, polymerizable systems, and products formed thereby |
| US10047192B2 (en) | 2012-06-01 | 2018-08-14 | Sirrus, Inc. | Optical material and articles formed therefrom |
| US9752059B2 (en) | 2012-11-16 | 2017-09-05 | Sirrus, Inc. | Plastics bonding systems and methods |
| US10607910B2 (en) | 2012-11-30 | 2020-03-31 | Sirrus, Inc. | Composite compositions for electronics applications |
| US9522381B2 (en) | 2013-01-11 | 2016-12-20 | Sirrus, Inc. | Method to obtain methylene malonate via bis(hydroxymethyl) malonate pathway |
| US10086355B2 (en) | 2013-01-11 | 2018-10-02 | Sirrus, Inc. | Method to obtain methylene malonate via bis(hydroxymethyl) malonate pathway |
| US10081685B2 (en) | 2014-09-08 | 2018-09-25 | Sirrus, Inc. | Emulson polymers including one or more 1,1-disubstituted alkene compounds, emulson methods, and polymer compositions |
| US9279022B1 (en) | 2014-09-08 | 2016-03-08 | Sirrus, Inc. | Solution polymers including one or more 1,1-disubstituted alkene compounds, solution polymerization methods, and polymer compositions |
| US9637564B2 (en) | 2014-09-08 | 2017-05-02 | Sirrus, Inc. | Emulsion polymers including one or more 1,1-disubstituted alkene compounds, emulsion methods, and polymer compositions |
| US9676875B2 (en) | 2014-09-08 | 2017-06-13 | Sirrus, Inc. | Solution polymers including one or more 1,1-disubstituted alkene compounds, solution polymerization methods, and polymer compositions |
| US11021617B2 (en) | 2014-09-08 | 2021-06-01 | Sirrus, Inc. | Polymers including one or more 1,1-disubstituted alkene compounds and polymer compositions thereof |
| US9249265B1 (en) | 2014-09-08 | 2016-02-02 | Sirrus, Inc. | Emulsion polymers including one or more 1,1-disubstituted alkene compounds, emulsion methods, and polymer compositions |
| US10519257B2 (en) | 2014-09-08 | 2019-12-31 | Sirrus, Inc. | Compositions containing 1,1-di-carbonyl-substituted alkene compounds for preparing polymers having enhanced glass transition temperatures |
| US9315597B2 (en) | 2014-09-08 | 2016-04-19 | Sirrus, Inc. | Compositions containing 1,1-disubstituted alkene compounds for preparing polymers having enhanced glass transition temperatures |
| US9790295B2 (en) | 2014-09-08 | 2017-10-17 | Sirrus, Inc. | Compositions containing 1,1-disubstituted alkene compounds for preparing polymers having enhanced glass transition temperatures |
| US10167348B2 (en) | 2014-09-08 | 2019-01-01 | Sirrus, Inc. | Solution polymers formed from methylene malonate monomers, polymerization, and solution polymer products |
| US9890227B1 (en) | 2014-09-08 | 2018-02-13 | Sirrus, Inc. | Compositions containing 1,1-di-substituted alkene compounds for preparing polymers having enhanced glass transition temperatures |
| US10184073B2 (en) | 2014-09-08 | 2019-01-22 | Sirrus, Inc. | Emulsion including polymers containing a 1,1-disubstituted alkene compound, adhesives, coatings, and methods thereof |
| US10308802B2 (en) | 2014-09-08 | 2019-06-04 | Sirrus, Inc. | Polymers including one or more 1,1-disubstituted alkene compounds and polymer compositions thereof |
| US9969819B2 (en) | 2014-09-08 | 2018-05-15 | Sirrus, Inc. | Pressure sensitive adhesive including a 1,1-disubstituted alkene compound |
| US9416091B1 (en) | 2015-02-04 | 2016-08-16 | Sirrus, Inc. | Catalytic transesterification of ester compounds with groups reactive under transesterification conditions |
| US9938223B2 (en) | 2015-02-04 | 2018-04-10 | Sirrus, Inc. | Catalytic transesterification of ester compounds with groups reactive under transesterification conditions |
| US10501400B2 (en) | 2015-02-04 | 2019-12-10 | Sirrus, Inc. | Heterogeneous catalytic transesterification of ester compounds with groups reactive under transesterification conditions |
| US9334430B1 (en) | 2015-05-29 | 2016-05-10 | Sirrus, Inc. | Encapsulated polymerization initiators, polymerization systems and methods using the same |
| US9683147B2 (en) | 2015-05-29 | 2017-06-20 | Sirrus, Inc. | Encapsulated polymerization initiators, polymerization systems and methods using the same |
| US10087272B2 (en) | 2015-05-29 | 2018-10-02 | Sirrus, Inc. | Encapsulated polymerization initiators, polymerization systems and methods using the same |
| US9217098B1 (en) | 2015-06-01 | 2015-12-22 | Sirrus, Inc. | Electroinitiated polymerization of compositions having a 1,1-disubstituted alkene compound |
| US9617354B2 (en) | 2015-06-01 | 2017-04-11 | Sirrus, Inc. | Electroinitiated polymerization of compositions having a 1,1-disubstituted alkene compound |
| US9518001B1 (en) | 2016-05-13 | 2016-12-13 | Sirrus, Inc. | High purity 1,1-dicarbonyl substituted-1-alkenes and methods for their preparation |
| US9567475B1 (en) | 2016-06-03 | 2017-02-14 | Sirrus, Inc. | Coatings containing polyester macromers containing 1,1-dicarbonyl-substituted 1 alkenes |
| US10196481B2 (en) | 2016-06-03 | 2019-02-05 | Sirrus, Inc. | Polymer and other compounds functionalized with terminal 1,1-disubstituted alkene monomer(s) and methods thereof |
| US10428177B2 (en) | 2016-06-03 | 2019-10-01 | Sirrus, Inc. | Water absorbing or water soluble polymers, intermediate compounds, and methods thereof |
| US9617377B1 (en) | 2016-06-03 | 2017-04-11 | Sirrus, Inc. | Polyester macromers containing 1,1-dicarbonyl-substituted 1 alkenes |
| US9745413B1 (en) | 2016-06-03 | 2017-08-29 | Sirrus, Inc. | Polyester macromers containing 1,1-dicarbonyl-substituted 1 alkenes |
| US9718989B1 (en) | 2016-06-03 | 2017-08-01 | Sirrus, Inc. | Coatings containing polyester macromers containing 1,1-dicarbonyl-substituted 1 alkenes |
| US10087283B2 (en) | 2016-06-03 | 2018-10-02 | Sirrus, Inc. | Polyester macromers containing 1,1-dicarbonyl-substituted 1 alkenes |
| US10150886B2 (en) | 2016-06-03 | 2018-12-11 | Sirrus, Inc. | Coatings containing polyester macromers containing 1,1-dicarbonyl-substituted 1 alkenes |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP2008174494A (en) | Methylenemalonic acid composition and method for stabilizing the same | |
| RU2484099C2 (en) | Method of stabilising unsaturated olefin monomers, monomer composition and retardant-containing composition | |
| US9284262B2 (en) | Process for preparing esteramide compounds | |
| JP2015007142A (en) | Production of ethylenically unsaturated acids or esters thereof | |
| JP2007238614A (en) | Polymerization inhibitor for stabilizing olefinically unsaturated monomer | |
| EP0127356B1 (en) | A 2,2,6,6-tetramethylpiperidine derivative, its production and its use as a stabilizer for synthetic resins | |
| JPH05310640A (en) | Production of hydroxyphenylcarboxylate | |
| US5047461A (en) | Butadiene polymer composition contains phenolic compound and sulfur-containing compound | |
| US10479757B2 (en) | N,N-dimethylaminoethyl acrylate composition stabilized in respect of discoloring effects | |
| CZ61495A3 (en) | Process for preparing esters of hydroxyphenylcarboxylic acids | |
| JPH09316026A (en) | Prevention of polymerization of (meth)acrylic acid and its ester | |
| JP3825518B2 (en) | Method for preventing polymerization of (meth) acrylic acid and its ester | |
| JPH0253438B2 (en) | ||
| JPH11152244A (en) | Aliphatic alkanal composition and improvement in storage stability of the compound | |
| US4448915A (en) | Acetylene carbamide derivatives, processes for their production, and antioxidants for organic substances which comprise such derivatives as active ingredients | |
| EP3064486B1 (en) | Phenyl(meta)acrylate production method and phenyl(meta)acrylate composition | |
| US6011173A (en) | Stabilization of thioacetic acid | |
| EP0763518B1 (en) | Stabilization method of vinyl compound with hydroxy group and composition containing such vinyl compound | |
| JP5890059B1 (en) | Method for separating 4-hydroxystyrene compound | |
| JPH11506141A (en) | Treatment to prevent polymerization of vinyl aromatic monomers | |
| JP2010132817A (en) | Carbazole group-containing (meth)acrylate and production method of the same | |
| JPH01180855A (en) | Hydroquinone compound and synthetic resin stabilizer containing said compound as active component | |
| US2848345A (en) | Paraffin wax stabilized with a 2, 4, 5, trihydroxyphenyl ketone | |
| JP3120037B2 (en) | Method for stabilizing hydroxyl-containing vinyl compound and composition containing hydroxyl-containing vinyl compound | |
| JP2013531640A (en) | Method for preparing ester amide compounds |