JP2006063010A - Method for preventing polymerization of 2,3-dihydroxypropyl-(meth)acrylamide - Google Patents
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Abstract
Description
本発明は、２，３−ジヒドロキシプロピル−（メタ）アクリルアミドの重合防止方法に関する。 The present invention relates to a method for preventing polymerization of 2,3-dihydroxypropyl- (meth) acrylamide.
２，３−ジヒドロキシプロピル−（メタ）アクリルアミドは、次に示す方法により製造されることが知られている。
（１）２，３−ジヒドロキシプロピルアミンをアセトン中でアクリロイルクロライドまたはメタクロイルクロライドと反応させる方法（非特許文献１）。
（２）グリシジル（メタ）アクリレートとアンモニアをエタノール、アセトン、ジオキサン、またはテトラヒドロフラン中で反応させる方法（特許文献１）。
(1) A method of reacting 2,3-dihydroxypropylamine with acryloyl chloride or methacryloyl chloride in acetone (Non-patent Document 1).
(2) A method in which glycidyl (meth) acrylate and ammonia are reacted in ethanol, acetone, dioxane, or tetrahydrofuran (Patent Document 1).
前記（１）の方法は、原料である２，３−ジヒドロキシプロピルアミンを塩酸キャッチ剤として使用し、副生する２，３−ジヒドロキシプロピルアミン・塩酸塩を濾過にて除くとういう煩雑な操作が必要であるとともに、減圧蒸留により精製された（メタ）アクリルアミドプロパンー２，３−ジオールの収率が低い。また、前記（２）の方法を記載した特公昭４８−１９２９５公報には、グリシジル（メタ）アクリレートとアンモニアを反応させて得られるＮ（２・３ジヒドロキシプロピル）（メタ）アクリルアミドを同様に減圧蒸留により取り出しているが、目的物の収率は記載されていない。 In the method (1), the raw material 2,3-dihydroxypropylamine is used as a hydrochloric acid catching agent, and the complicated operation of removing by-product 2,3-dihydroxypropylamine / hydrochloride by filtration is performed. The yield of (meth) acrylamide propane-2,3-diol, which is necessary and purified by vacuum distillation, is low. In Japanese Patent Publication No. 48-19295, which describes the method of (2), N (2.3 dihydroxypropyl) (meth) acrylamide obtained by reacting glycidyl (meth) acrylate and ammonia is similarly distilled under reduced pressure. The yield of the target product is not described.
本発明者らは、前記（２）の方法である、グリシジル（メタ）アクリレートとアンモニアの反応を検討した結果、反応に用いた溶媒を４０℃以下で除去して得られた生成物中にはＮ（２・３ジヒドロキシプロピル）（メタ）アクリルアミドの他にゲル状物質が含まれていることを確認した。 As a result of studying the reaction of glycidyl (meth) acrylate and ammonia, which is the method of (2), the present inventors have found that the product obtained by removing the solvent used for the reaction at 40 ° C. or less includes It was confirmed that a gel substance was contained in addition to N (2.3 dihydroxypropyl) (meth) acrylamide.
本発明者らは、前記（１）の方法での収率および（２）の方法では、グリシジル（メタ）アクリレートとアンモニアとの反応の進行中および目的物を減圧蒸留により精製する工程でゲル状物質、即ちＮ（２・３ジヒドロキシプロピル）（メタ）アクリルアミドの重合体が生成していると推測している。 In the process of (1) and the process of (2), the present inventors obtained a gel-like product during the reaction of glycidyl (meth) acrylate with ammonia and in the process of purifying the target product by vacuum distillation. It is presumed that a substance, that is, a polymer of N (2.3 dihydroxypropyl) (meth) acrylamide is formed.
したがって、本発明は、２，３−ジヒドロキシプロピル−（メタ）アクリルアミドの重合防止方法を提供することを目的とする。 Therefore, an object of the present invention is to provide a method for preventing polymerization of 2,3-dihydroxypropyl- (meth) acrylamide.
炭素―炭素二重結合を有する不飽和化合物の製造、保存、及び輸送等においては、酸素酸化による着色等を防止する為に、酸素は極力排除され、不活性ガス雰囲気下で行われるのが一般的である。
本発明者らは、２，３−ジヒドロキシプロピル（メタ）アクリルアミドの製造、保存、及び輸送方法について検討を重ねた結果、所定量の酸素を溶存する２，３−ジヒドロキシプロピル（メタ）アクリルアミドは、その重合体を生成せず着色もしないことを見出し、本発明に到達した。
In the production, storage, and transportation of unsaturated compounds having a carbon-carbon double bond, oxygen is generally excluded in an inert gas atmosphere in order to prevent coloring due to oxygen oxidation. Is.
As a result of studying the production, storage, and transportation methods of 2,3-dihydroxypropyl (meth) acrylamide, the present inventors have determined that 2,3-dihydroxypropyl (meth) acrylamide in which a predetermined amount of oxygen is dissolved is: The inventors have found that the polymer is not produced and is not colored, and the present invention has been reached.
すなわち、本発明は、酸素を溶存させることを特徴とする、一般式（１） That is, the present invention is characterized in that oxygen is dissolved, and is represented by the general formula (1)
（Ｒは、水素原子またはメチル基を表す。）で表される化合物の重合防止方法
に関するものである。
(Wherein R represents a hydrogen atom or a methyl group).
本発明によれば、一般式（１）で表される化合物の重合防止方法を提供することができる。 According to the present invention, it is possible to provide a method for preventing polymerization of the compound represented by the general formula (1).
本発明の一般式（１）で表される化合物の重合防止方法は、一般式（１）で表される化合物に酸素を溶存させることを特徴とする。 The method for preventing polymerization of the compound represented by the general formula (1) of the present invention is characterized in that oxygen is dissolved in the compound represented by the general formula (1).
一般式（１）中のＲは、水素原子またはメチル基を表す。 R in the general formula (1) represents a hydrogen atom or a methyl group.
一般式（１）で表される化合物に溶存させる酸素は、酸素自体の他、酸素と一般式（１）で表される化合物と反応しない化合物との混合物をその供給源とすることができる。 The oxygen dissolved in the compound represented by the general formula (1) can be supplied from a mixture of oxygen and a compound that does not react with the compound represented by the general formula (1) in addition to oxygen itself.
一般式（１）で表される化合物と反応しない化合物としては、例えば、一酸化炭素、二酸化炭素、窒素、ネオン、アルゴン等の不活性ガスを好ましいものとして例示することができる。 As a compound which does not react with the compound represented by General formula (1), inert gas, such as carbon monoxide, a carbon dioxide, nitrogen, neon, argon, can be illustrated as a preferable thing, for example.
酸素と一般式（１）で表される化合物と反応しない化合物との混合物としては、空気が経済的で好ましい。 As a mixture of oxygen and the compound that does not react with the compound represented by the general formula (1), air is economical and preferable.
一般式（１）で表される化合物に酸素を溶存させる方法として制限はないが、例えば、酸素、または酸素と一般式（１）で表される化合物と反応しない化合物との混合物を一般式（１）で表される化合物に吹き込む方法、または酸素、または酸素と一般式（１）で表される化合物と反応しない化合物との混合物の存在下で一般式（１）で表される化合物を撹拌する方法が挙げられる。 The method for dissolving oxygen in the compound represented by the general formula (1) is not limited. For example, oxygen or a mixture of oxygen and a compound that does not react with the compound represented by the general formula (1) is represented by the general formula ( A method of blowing into the compound represented by 1), or stirring the compound represented by the general formula (1) in the presence of oxygen or a mixture of oxygen and a compound that does not react with the compound represented by the general formula (1) The method of doing is mentioned.
一般式（１）で表される化合物の重合を防止するには、一般式（１）で表される化合物中に溶存酸素濃度が少なくとも０．１ｍｇ／ｌ必要である。 In order to prevent polymerization of the compound represented by the general formula (1), the dissolved oxygen concentration in the compound represented by the general formula (1) needs to be at least 0.1 mg / l.
一般式（１）で表される化合物中の溶存酸素濃度は圧力および温度に依存するが、例えば、一般式（１）で表される化合物及びそれを含む溶液を冷暗所で保存（５〜１５℃、遮光、１気圧）する場合、溶存酸素濃度が０．１０〜０．５０ｍｇ／ｌの範囲であれば重合体の生成はほとんど起こらない。 The dissolved oxygen concentration in the compound represented by the general formula (1) depends on the pressure and temperature. For example, the compound represented by the general formula (1) and a solution containing the compound are stored in a cool and dark place (5 to 15 ° C. , Shading, 1 atm), almost no polymer is generated if the dissolved oxygen concentration is in the range of 0.10 to 0.50 mg / l.
酸素を溶存させるとともに、ラジカル補足剤、酸化防止剤、ＨＡＬＳ（ヒンダードアミン光安定剤）等の公知の添加剤を添加して一般式（１）で表される化合物の重合を防止することもできる。 While dissolving oxygen, known additives such as radical scavengers, antioxidants, and HALS (hindered amine light stabilizers) can be added to prevent polymerization of the compound represented by the general formula (1).
これらの添加剤の中ではフェノール類が好ましく、特にベンゼン環に少なくとも１個のヒドロキシ基が結合した一般式（２） Among these additives, phenols are preferable, and in particular, the general formula (2) in which at least one hydroxy group is bonded to the benzene ring.
（Ｒ３は、水素原子、炭素数１〜４のアルキル基、炭素数１〜４のアルコキシ基または水酸基を表し、Ｒ１、Ｒ２、Ｒ４およびＲ５は、それぞれ水素原子または炭素数１〜４のアルキル基を表す。）で表される化合物が好ましい。 (R 3 represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms or a hydroxyl group, and R 1 , R 2 , R 4 and R 5 are each a hydrogen atom or 1 carbon atom. Represents an alkyl group of ˜4.).
一般式（２）に於て炭素数１〜４のアルコキシ基としては、例えば、メトキシ基、エトキシ基等が挙げられる。同様に炭素数１〜４のアルキル基としては、例えば、メチル基、エチル基、ターシャリーブチル基等が挙げられる。 In the general formula (2), examples of the alkoxy group having 1 to 4 carbon atoms include a methoxy group and an ethoxy group. Similarly, examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, and a tertiary butyl group.
一般式（２）で表される化合物として具体的化合物を例示するとすれば、例えば、ヒドロキノン、４−メトキシフェノール、４−エトキシフェノール、２−ｔ−ブチル−４−メトキシフェノール、３−ｔ−ブチル−４−メトキシフェノール、２，６−ジ−ｔ−ブチルフェノール、２−ｔ−ブチル−４−メチルフェノール、２−ｔ−ブチル−４−エチルフェノール、２，６−ジ−ｔ−ブチル−４−メチルフェノール、２，６−ジ−ｔ−ブチル−４−エチルフェノール等が挙げられる。 If a specific compound is illustrated as a compound represented by General formula (2), for example, hydroquinone, 4-methoxyphenol, 4-ethoxyphenol, 2-t-butyl-4-methoxyphenol, 3-t-butyl -4-methoxyphenol, 2,6-di-t-butylphenol, 2-t-butyl-4-methylphenol, 2-t-butyl-4-ethylphenol, 2,6-di-t-butyl-4- And methylphenol and 2,6-di-t-butyl-4-ethylphenol.
これらフェノール類の添加量は、一般式（１）で表される化合物に対して、
０．０１〜３．０モル％が好ましく、０．０５〜０．５モル％であればより好ましい。
The added amount of these phenols is relative to the compound represented by the general formula (1).
0.01 to 3.0 mol% is preferable, and 0.05 to 0.5 mol% is more preferable.
一般式（１）で表される化合物の製造方法に制限はないが、例えば、前記の背景技術の項に記載した２つの製造方法が挙げられる。 Although there is no restriction | limiting in the manufacturing method of the compound represented by General formula (1), For example, the two manufacturing methods described in the above-mentioned background art section are mentioned.
一般式（１）で表される化合物を酸素の存在下で製造することにより、製造中に一般式（１）で表される化合物の重合を防止することができる。 By producing the compound represented by the general formula (1) in the presence of oxygen, polymerization of the compound represented by the general formula (1) can be prevented during the production.
例えば、前記の背景技術の項に記載した２つの製造方法において、反応工程及び精製工程中の一般式（１）で表される化合物またはこれを含む溶液中の溶存酸素濃度が少なくとも０．１ｍｇ／ｌとなるようにすれば一般式（１）で表される化合物の重合を防止することができるが、大気圧下、室温付近では１０ｍｇ／ｌ以上溶解させることは困難である。 For example, in the two production methods described in the background section above, the dissolved oxygen concentration in the compound represented by the general formula (1) in the reaction step and the purification step or a solution containing the compound is at least 0.1 mg / If it is set to 1, it can prevent superposition | polymerization of the compound represented by General formula (1), However It is difficult to make 10 mg / l or more melt | dissolve near room temperature under atmospheric pressure.
一般式（１）で表される化合物またはこれを含む溶液中の溶存酸素濃度を高める方法として、加圧して溶解する方法があるが、煩雑で付帯設備を必要とする為、非経済的である。 As a method for increasing the dissolved oxygen concentration in the compound represented by the general formula (1) or a solution containing the compound, there is a method of dissolving by pressurization, but it is complicated and requires ancillary facilities, which is uneconomical. .
減圧下での蒸留以外は大気圧下で製造・保存・輸送する方法が妥当である。 Other than distillation under reduced pressure, a method of production, storage and transportation under atmospheric pressure is appropriate.
即ち、一般式（１）で表される化合物またはこれを含む溶液の製造、保存、及び輸送時の溶存酸素濃度は、０．１〜１０ｍｇ／ｌの範囲が現実的且つ経済的で好ましい。 That is, the concentration of dissolved oxygen during production, storage, and transportation of the compound represented by the general formula (1) or a solution containing the compound is preferably in the range of 0.1 to 10 mg / l because it is realistic and economical.
反応工程の系内に酸素を存在させる方法としては、例えば、空気雰囲気下で反応を行う方法、または空気を反応系内にバブリングしながら反応を行う方法が好ましい。 As a method for causing oxygen to be present in the reaction process system, for example, a method in which the reaction is performed in an air atmosphere or a method in which the reaction is performed while bubbling air into the reaction system is preferable.
精製工程の系内に酸素を存在させる方法としては、空気雰囲気下で操作する方法が好ましい。但し、脱溶媒及び蒸留等の濃縮操作に於ては、加熱と基質濃度向上により特に重合が起こり易い為、空気雰囲気下で操作するだけでは不充分な場合があり、例えば、蒸留器内の溶液中に空気をバブリングさせながら濃縮する方法がより好ましい。 As a method for allowing oxygen to be present in the system of the purification step, a method of operating in an air atmosphere is preferable. However, in concentration operations such as solvent removal and distillation, polymerization is particularly likely to occur due to heating and substrate concentration enhancement, so it may not be sufficient to operate only in an air atmosphere. A method of concentrating while bubbling air is more preferable.
保存及び輸送時に酸素を存在させる方法としては、例えば、空気をバブリングさせた後に保存及び輸送を行う方法、または大気を封入して保存及び輸送を行う方法等が好ましい。
一般式（１）で表される化合物の製造方法として、酸素の存在下でグリシジル（メタ）アクリレートとアンモニアとを反応させる一般式（１）表される化合物の製造方法は簡便な方法であるため好ましい方法である。
As a method for allowing oxygen to exist during storage and transportation, for example, a method of performing storage and transportation after bubbling air, a method of performing storage and transportation by enclosing air, and the like are preferable.
As a method for producing the compound represented by the general formula (1), the method for producing the compound represented by the general formula (1) in which glycidyl (meth) acrylate and ammonia are reacted in the presence of oxygen is a simple method. This is the preferred method.
この製造方法に添加剤としてヒドロキノンを用いると、得られる一般式（１）表される化合物およびヒドロキノンを含む最終製品が赤く着色することがあるため、無色透明な最終製品が要求される場合には、ヒドロキノン以外のフェノール類を反応に用いるのが好ましい。
従来の一般式（１）で表される化合物の製造方法では、一般式（１）で表される化合物とともにその重合体（ゲル状物質）が生成する場合があるため、このゲル状物質と分離するために反応終了後の反応混合物から一般式（１）で表される化合物を減圧蒸留により精製して回収する必要がある。
When hydroquinone is used as an additive in this production method, the resulting final product containing the compound represented by the general formula (1) and hydroquinone may be colored red. It is preferable to use phenols other than hydroquinone for the reaction.
In the conventional method for producing the compound represented by the general formula (1), the polymer (gel-like substance) may be generated together with the compound represented by the general formula (1). Therefore, it is necessary to purify and recover the compound represented by the general formula (1) by distillation under reduced pressure from the reaction mixture after completion of the reaction.
これに対して、本発明の方法によれば、一般式（１）で表される化合物の重合が防止されるため、従来の一般式（１）で表される化合物の回収方法、すなわち、一般式（１）で表される化合物を含む反応混合物から過剰のアンモニアおよび反応に用いられる溶媒を除去した後、一般式（１）で表される化合物を減圧蒸留により精製して回収する方法に換えて、一般式（１）で表される化合物を含む反応混合物から過剰のアンモニアおよび反応に用いられる溶媒を除去して得られる残留物を最終製品とすることができる。なお、最終製品中にはその使用目的によっては反応に用いられる溶媒が含まれていても差し支えない。 On the other hand, according to the method of the present invention, since the polymerization of the compound represented by the general formula (1) is prevented, the conventional method for recovering the compound represented by the general formula (1), that is, After removing excess ammonia and the solvent used for the reaction from the reaction mixture containing the compound represented by the formula (1), the compound represented by the general formula (1) is purified by vacuum distillation and recovered. The residue obtained by removing excess ammonia and the solvent used in the reaction from the reaction mixture containing the compound represented by the general formula (1) can be used as a final product. The final product may contain a solvent used in the reaction depending on the purpose of use.
この最終製品中には、一般式（１）で表される化合物の製造時に前記の添加剤を用いる場合は、一般式（１）で表される化合物中に添加剤を含むが、この添加剤を含む最終製品はそのまま他の重合性化物との重合反応に用いることができる。
例えば、一般式（１）で表される化合物を含む最終製品と３−メタクリロイルオキシ−２−ヒドロキシ−１−アクリロイルオキシ−プロパン等の不飽和二重結合を有する重合性化合物を用いて、一般式（１）で表される化合物と不飽和二重結合を有する重合性化合物との共重合体を得ることができる。
In the final product, when the above-described additive is used during the production of the compound represented by the general formula (1), the additive is contained in the compound represented by the general formula (1). The final product containing can be used as it is for the polymerization reaction with other polymerizable compounds.
For example, the final product containing the compound represented by the general formula (1) and a polymerizable compound having an unsaturated double bond such as 3-methacryloyloxy-2-hydroxy-1-acryloyloxy-propane are used. A copolymer of the compound represented by (1) and a polymerizable compound having an unsaturated double bond can be obtained.
また、前記の方法により得られる酸素を溶存する一般式（１）で表される化合物は、保存時及び輸送時の重合による変質を防止することができる。 In addition, the compound represented by the general formula (1) in which oxygen obtained by the above method is dissolved can prevent deterioration due to polymerization during storage and transportation.
本発明の方法は、２，３−ジヒドロキシプロピル（メタ）アクリルアミドの製造時および保存時の重合を防止するのに有用であり、また、２，３−ジヒドロキシプロピル（メタ）アクリルアミド自体の重合体を含まない２，３−ジヒドロキシプロピル（メタ）アクリルアミドは、水溶性高分子、塗料、繊維の改質剤、紙、土壌改良剤などの原料として有用である。 The method of the present invention is useful for preventing polymerization during the production and storage of 2,3-dihydroxypropyl (meth) acrylamide, and also provides a polymer of 2,3-dihydroxypropyl (meth) acrylamide itself. The 2,3-dihydroxypropyl (meth) acrylamide that is not contained is useful as a raw material for water-soluble polymers, paints, fiber modifiers, paper, soil improvers, and the like.
以下、実施例により本発明をさらに詳細に説明するが、本発明がこれら実施例のみに限定されるものではない。
尚、実施例及び比較例について特に断りがない限り、大気雰囲気下で室温にて操作した。また、実施例及び比較例の評価は以下の方法で行った。
EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited only to these Examples.
In addition, unless there was particular notice about the Example and the comparative example, it operated at room temperature in the air atmosphere. In addition, evaluation of Examples and Comparative Examples was performed by the following methods.
＜溶存酸素濃度の測定＞
飯島電子工業（株）製品名ＤＯメータ，型式ＩＤ−１００を用いて測定した。
尚、測定は、静置して気泡を除いた状態で行った。
<Measurement of dissolved oxygen concentration>
It measured using Iijima Electronics Co., Ltd. product name DO meter, model ID-100.
In addition, the measurement was performed in a state where the air bubbles were removed by standing.
＜ゲル状物質の確認＞
ゲル状物質の確認は、下記の２通りのいずれの方法で行い、いずれの方法でも不溶物が観測されない場合に、ゲル状物質は確認されないと判定した。
（１）最終製品を無色透明のガラス容器に移液し、静置後、ガラス容器内の液中にシュリーレン状の不溶物があるか否かを観測する。
（２）最終製品をメタノールにて希釈（製品濃度１０ｖｏｌ％）し、希釈溶液中に不溶物があるか否かを観測する。
<Confirmation of gel substance>
The gel-like substance was confirmed by any of the following two methods, and when no insoluble matter was observed by any of the methods, it was determined that no gel-like substance was confirmed.
(1) The final product is transferred to a colorless and transparent glass container, and after standing, it is observed whether or not there is a schlieren-like insoluble substance in the liquid in the glass container.
(2) Dilute the final product with methanol (product concentration: 10 vol%), and observe whether there is any insoluble matter in the diluted solution.
＜水接触角の測定＞
協和界面科学社製ＣＡ−Ｖ型を用いて、室温（２５℃）で測定し、測定対象材料上の水滴について、任意５点の測定結果の平均値を記載した。
<Measurement of water contact angle>
It measured at room temperature (25 degreeC) using Kyowa Interface Science company CA-V type | mold, and described the average value of the measurement result of arbitrary 5 points | pieces about the water drop on a measuring object material.
［実施例１］
２，３−ジヒドロキシプロピル−メタクリルアミドの製造
大気雰囲気下、反応フラスコにメタノール１８００ｍｌを装入し、氷水浴下、アンモニアガスをバブリングさせて１１４ｇ（６．７０モル）をメタノールに吸収させた。
[Example 1]
Production of 2,3-dihydroxypropyl-methacrylamide In an air atmosphere, 1800 ml of methanol was charged into a reaction flask, and ammonia gas was bubbled in an ice water bath to absorb 114 g (6.70 mol) in methanol.
次に、アンモニアガスを１ｌ／ｍｉｎでバブリングしながら、グリシジルメタクリレート１０１２ｇ（７．１２モル）に添加剤として４−メトキシフェノール１．０ｇ（０．１１モル％対グリシジルメタクリレート）を加えた混合溶液を、内温３５〜４５の範囲にコントロールしながら１時間かけて滴下し、滴下終了と同時にアンモニアガスのバブリングを止め、４０℃で６時間熟成した。この反応終了液中の溶存酸素濃度は１．９ｍｇ／ｌであった。 Next, a mixed solution in which 1.0 g of 4-methoxyphenol (0.11 mol% to glycidyl methacrylate) was added as an additive to 1012 g (7.12 mol) of glycidyl methacrylate while bubbling ammonia gas at 1 l / min. The solution was added dropwise over 1 hour while controlling the internal temperature within the range of 35 to 45, and the bubbling of ammonia gas was stopped simultaneously with the completion of the addition, followed by aging at 40 ° C. for 6 hours. The dissolved oxygen concentration in this reaction-terminated liquid was 1.9 mg / l.
反応に使用したアンモニアガスの総量は、１６０ｇ（９．４０モル、１．３２倍モル対グリシジルメタクリレート）であった。 The total amount of ammonia gas used in the reaction was 160 g (9.40 moles, 1.32 moles versus glycidyl methacrylate).
得られた反応液に添加剤として４−メトキシフェノール１．０ｇ（０．１１モル％対グリシジルメタクリレート）を追加し、減圧下（〜２０ｍｍＨｇ）で液層部に大気をバブリングさせながら３０℃で溶媒を留去した。メタノールが凡そ１０００ｍｌ留去した時点の溶存酸素は０．３０ｍｇ／ｌであった。 To the obtained reaction liquid, 1.0 g of 4-methoxyphenol (0.11 mol% with respect to glycidyl methacrylate) was added as an additive, and the solvent was added at 30 ° C. while bubbling air into the liquid layer part under reduced pressure (˜20 mmHg). Was distilled off. When about 1000 ml of methanol was distilled off, the dissolved oxygen was 0.30 mg / l.
引き続き大気バブリングを続行しながら減圧度を上げて（〜１ｍｍＨｇ）、室温にてさらに溶媒を留去した。残った蒸留残渣中の溶存酸素濃度は０．１２ｍｇ／ｌであった。 Subsequently, the degree of vacuum was increased while continuing atmospheric bubbling (˜1 mmHg), and the solvent was further distilled off at room temperature. The dissolved oxygen concentration in the remaining distillation residue was 0.12 mg / l.
最後に、この蒸留残渣を濾過して、メタノールを３．８ｗｔ％含む無色透明粘調性液体の２，３−ジヒドロキシプロピル−メタクリルアミド１００２ｇ（粗収率８８モル％対グリシジルメタクリレート）を濾液として得た。得られた粘調性液体には、ゲル状物質は確認されなかった。 Finally, the distillation residue was filtered to obtain 1002 g of 2,3-dihydroxypropyl-methacrylamide as a colorless transparent viscous liquid containing 3.8 wt% of methanol (crude yield 88 mol% to glycidyl methacrylate) as a filtrate. It was. No gel-like substance was confirmed in the resulting viscous liquid.
結果を表１に掲載する。 The results are listed in Table 1.
［比較例１］
大気雰囲気下を窒素雰囲気下に変更し、大気バブリングを窒素バブリングに変更して実施例１と同様の試験を行った。
[Comparative Example 1]
The same test as in Example 1 was performed by changing the air atmosphere to a nitrogen atmosphere and changing the air bubbling to nitrogen bubbling.
その結果、溶媒を留去し終わった時点の蒸留残渣中の溶存酸素濃度は０．０８ｍｇ／ｌで、２，３−ジヒドロキシプロピル−メタクリルアミドを含む無色透明粘調性液体１００４ｇ（粗収率８９モル％対グリシジルメタクリレート）が濾液として得られたが、一部ゲル状物質を含んでいた。 As a result, the dissolved oxygen concentration in the distillation residue at the time when the solvent was distilled off was 0.08 mg / l, and 1004 g of a colorless transparent viscous liquid containing 2,3-dihydroxypropyl-methacrylamide (crude yield 89 Mol% to glycidyl methacrylate) was obtained as the filtrate, but partially contained gelled material.
ゲル状物質を含む上記の粘調性液体から１３０ｇを蒸留フラスコに移液し、減圧下で（＜１ｍｍＨｇ）加熱（〜１８０℃）蒸留して、生成物を留分として６０．０ｇ回収し、得られた留分をガスクロマトグラフィー（以下、「ＧＣ」と略記する。）分析した。ＧＣ分析条件は次のとおりである。
ＧＣ分析条件
カラム；BPX-35 φ0.22mm×50m 膜厚0.25μm （エス・シ゛ー・イー シ゛ャハ゜ン株式会社）
キャリアカ゛ス；ヘリウム 線速 0.5m/min スフ゜リット1/20
カラムオーフ゛ン温度；50℃×5min → 320℃×2min 昇温速度15℃/min
注入口温度；200℃ 検出器及び検出器温度；FID 350℃
得られた留分の２，３−ジヒドロキシプロピル−メタクリルアミドの純度は僅か３３ GC area％であった。
これに対して、実施例１で得られた最終製品の純度分析を同じく前記のＧＣ分析条件で行ったところ、９１ GC area％であった。
From the viscous liquid containing the gel substance, 130 g was transferred to a distillation flask and heated (~ 1800C) under reduced pressure (<1 mmHg) to recover 60.0 g of the product as a fraction. The obtained fraction was analyzed by gas chromatography (hereinafter abbreviated as “GC”). The GC analysis conditions are as follows.
GC analysis condition column; BPX-35 φ0.22mm × 50m, film thickness 0.25μm (SJE Jyahan Co., Ltd.)
Carrier gas; helium Linear speed 0.5m / min Split 1/20
Column oven temperature: 50 ℃ × 5min → 320 ℃ × 2min Heating rate 15 ℃ / min
Inlet temperature: 200 ° C Detector and detector temperature: FID 350 ° C
The purity of 2,3-dihydroxypropyl-methacrylamide obtained was only 33 GC area%.
On the other hand, when the purity analysis of the final product obtained in Example 1 was performed under the same GC analysis conditions, it was 91 GC area%.
結果を表１に掲載する。 The results are listed in Table 1.
［実施例２］
実施例１を１００倍にスケールアップして得られた２，３−ジヒドロキシプロピル−メタクリルアミドを含む無色透明粘調性液体１００Ｋｇ（溶存酸素濃度０．１２ｍｇ／ｌ）を、内容積１９ｌのＰＰラミネート缶（藤井容器工業株式会社、品名；ハイクオリティー缶）に大気雰囲気下で１８Ｋｇ充填し、冷暗所（１０℃、遮光、大気圧下）にて保存した。
[Example 2]
A colorless transparent viscous liquid 100 kg (dissolved oxygen concentration 0.12 mg / l) containing 2,3-dihydroxypropyl-methacrylamide obtained by scaling up Example 1 100 times was applied to a PP laminate having an internal volume of 19 l. A can (Fujii Container Industry Co., Ltd., product name; high quality can) was filled with 18 kg in an air atmosphere and stored in a cool dark place (10 ° C., shading, under atmospheric pressure).
４ヶ月後、保存液の溶存酸素濃度は０．１２ｍｇ／ｌであり、充填時と同様に無色透明の粘調性液体でゲル状物質は確認されなかった。 Four months later, the dissolved oxygen concentration of the preservation solution was 0.12 mg / l, and no gel-like substance was confirmed in the colorless and transparent viscous liquid as in the filling.
結果を表２に掲載する。 The results are listed in Table 2.
［実施例３］
２，３−ジヒドロキシプロピル−メタクリルアミドの酸素溶解度測定（室温、大気圧下）
大気雰囲気下、実施例２で得られた２，３−ジヒドロキシプロピル−メタクリルアミドを、２４℃にて恒量値に達するまで空気バブリングを行った。恒量値の溶存酸素濃度は０．４３ｍｇ／ｌであった。
[Example 3]
Measurement of oxygen solubility of 2,3-dihydroxypropyl-methacrylamide (room temperature, atmospheric pressure)
Under air atmosphere, 2,3-dihydroxypropyl-methacrylamide obtained in Example 2 was subjected to air bubbling at 24 ° C. until reaching a constant value. The dissolved oxygen concentration of the constant value was 0.43 mg / l.
［実施例４］
２，３−ジヒドロキシプロピル−メタクリルアミド溶液の酸素溶解度測定（室温、大気圧下）
大気雰囲気下、実施例２で得られた２，３−ジヒドロキシプロピル−メタクリルアミド２００ｇとメタノール１００ｇの混合溶液を、２４℃にて恒量値に達するまで空気バブリングを行った。恒量値の溶存酸素濃度は６．１ｍｇ／ｌであった。
[Example 4]
Measurement of oxygen solubility of 2,3-dihydroxypropyl-methacrylamide solution (room temperature, atmospheric pressure)
Under an air atmosphere, air bubbling was performed on the mixed solution of 2,3-dihydroxypropyl-methacrylamide 200 g obtained in Example 2 and 100 g of methanol at 24 ° C. until a constant value was reached. The dissolved oxygen concentration of the constant weight value was 6.1 mg / l.
［参考例１］
実施例１で得られた２，３−ジヒドロキシプロピル−メタクリルアミド８．０ｇ、３−メタクリロイルオキシ−２−ヒドロキシ−１−アクリロイルオキシ−プロパン１２．０ｇの混合液に、重合促進剤としてＮ，Ｎ−ジメチルアミノ−エチル−メタクリレート１．０ｇ（５ｗｔ％）、光重合開始剤としてエサキュアーＫＴＯ／４６（ランベルティー社製）０．１ｇ（０．５ｗｔ％）、熱重合開始剤としてｔ−ブチルパーオキシ−３，５，５−トリメチルヘキサノエート０．０４ｇ（０．２ｗｔ％）、内部離型剤としてビス（５−ｎ−ブトキシ−１，４−ジメチル−３−オキサペンチル）リン酸０．０６ｇ（０．３ｗｔ％）を加えて減圧下で混合脱泡し、組成物を調製した。
[Reference Example 1]
A mixture of 8.0 g of 2,3-dihydroxypropyl-methacrylamide obtained in Example 1 and 12.0 g of 3-methacryloyloxy-2-hydroxy-1-acryloyloxy-propane was mixed with N, N as a polymerization accelerator. -1.0 g (5 wt%) of dimethylamino-ethyl-methacrylate, 0.1 g (0.5 wt%) of Esacure KTO / 46 (Lamberti) as a photopolymerization initiator, and t-butylperoxy as a thermal polymerization initiator -3,5,5-trimethylhexanoate 0.04 g (0.2 wt%), bis (5-n-butoxy-1,4-dimethyl-3-oxapentyl) phosphoric acid 0.06 g as an internal mold release agent (0.3 wt%) was added and mixed and degassed under reduced pressure to prepare a composition.
この組成物を、樹脂製の粘着テープとガラス板からなるガラスモールドに移液し、紫外線を照射して硬化させ、次いで１００℃で２時間エージングした。冷却後、ガラスモールドから離型させて得られた重合体は、均一で透明な成形体であった。
得られた成型体の表面は手で触っても粘着性がなく、水接触角は２５°であった。
This composition was transferred to a glass mold composed of a resin adhesive tape and a glass plate, cured by irradiation with ultraviolet rays, and then aged at 100 ° C. for 2 hours. After cooling, the polymer obtained by releasing from the glass mold was a uniform and transparent molded body.
The surface of the obtained molding was not sticky even when touched by hand, and the water contact angle was 25 °.
Claims (2)
（Ｒは、水素原子またはメチル基を表す。）で表される化合物の重合防止方法。 General formula (1) characterized by dissolving oxygen
(R represents a hydrogen atom or a methyl group.) A method for preventing polymerization of a compound represented by:
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014139662A (en) * | 2012-12-19 | 2014-07-31 | Sekisui Chem Co Ltd | Sealing agent for liquid crystal dropping method, manufacturing method of sealing agent for liquid crystal dropping method, vertical conduction material, and liquid crystal display element |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4819295B1 (en) * | 1970-09-30 | 1973-06-12 | ||
| JPS62138460A (en) * | 1985-11-27 | 1987-06-22 | ソシエテ シミツク デ シヤルボナ−ジユ エス．ア−． | Novel synthesis of n-dialkylaminoalkyl(meth)acrylamide |
| JPH0539251A (en) * | 1991-08-02 | 1993-02-19 | Nitto Chem Ind Co Ltd | Production of crystalline n-methylolacrylamide |
| JPH0578293A (en) * | 1991-06-18 | 1993-03-30 | Showa Denko Kk | Production of concentrated acrylamide aqueous solution and apparatus therefor |
| JPH08176081A (en) * | 1994-12-22 | 1996-07-09 | Nitto Chem Ind Co Ltd | Production of n-alkoxymethyl(meth)acrylamide |
-
2004
- 2004-08-26 JP JP2004246746A patent/JP2006063010A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4819295B1 (en) * | 1970-09-30 | 1973-06-12 | ||
| JPS62138460A (en) * | 1985-11-27 | 1987-06-22 | ソシエテ シミツク デ シヤルボナ−ジユ エス．ア−． | Novel synthesis of n-dialkylaminoalkyl(meth)acrylamide |
| JPH0578293A (en) * | 1991-06-18 | 1993-03-30 | Showa Denko Kk | Production of concentrated acrylamide aqueous solution and apparatus therefor |
| JPH0539251A (en) * | 1991-08-02 | 1993-02-19 | Nitto Chem Ind Co Ltd | Production of crystalline n-methylolacrylamide |
| JPH08176081A (en) * | 1994-12-22 | 1996-07-09 | Nitto Chem Ind Co Ltd | Production of n-alkoxymethyl(meth)acrylamide |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014139662A (en) * | 2012-12-19 | 2014-07-31 | Sekisui Chem Co Ltd | Sealing agent for liquid crystal dropping method, manufacturing method of sealing agent for liquid crystal dropping method, vertical conduction material, and liquid crystal display element |
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