JPH0789915A - Purification of polar vinylic compound - Google Patents
Purification of polar vinylic compoundInfo
- Publication number
- JPH0789915A JPH0789915A JP23501193A JP23501193A JPH0789915A JP H0789915 A JPH0789915 A JP H0789915A JP 23501193 A JP23501193 A JP 23501193A JP 23501193 A JP23501193 A JP 23501193A JP H0789915 A JPH0789915 A JP H0789915A
- Authority
- JP
- Japan
- Prior art keywords
- vinyl compound
- polar vinyl
- group
- polar
- pressure
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は極性ビニル化合物の精製
法に関し、さらに詳しくは重合阻害物質と、少なくとも
１個の酸素原子、窒素原子または硫黄原子を有する極性
ビニル化合物との混合物、すなわち、重合阻害物質を含
有する極性ビニル化合物（以下粗極性ビニル化合物とい
う）を０〜１００℃で５００〜３０００気圧に加圧して
極性ビニル化合物の結晶を析出せしめ、加圧下において
極性ビニル化合物の結晶を液相から分離することによっ
て、高純度の極性ビニル化合物を得る方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for purifying a polar vinyl compound, more specifically, a mixture of a polymerization inhibitor and a polar vinyl compound having at least one oxygen atom, nitrogen atom or sulfur atom, that is, polymerization. A polar vinyl compound containing an inhibitor (hereinafter referred to as a crude polar vinyl compound) is pressurized at 0 to 100 ° C. to 500 to 3000 atm to precipitate crystals of the polar vinyl compound, and the crystals of the polar vinyl compound are in a liquid phase under pressure. To obtain a high-purity polar vinyl compound.
【０００２】[0002]
【従来の技術】ビニル化合物をラジカル重合、カチオン
重合、あるいはアニオン重合など付加重合することによ
り数多くの有用な高分子化合物が得られるが、この反応
は連鎖反応であるため、ビニル化合物の製造工程中など
に生成した連鎖停止作用あるいは連鎖移動作用を有する
化合物が含まれていると、重合反応が遅くなったり、分
子量の低下するなど悪影響が生ずる。これらの重合性阻
害物質は極めて微量で重合反応に作用するものが多く、
このため、ビニル化合物に優れた重合性を付与するに
は、これらの重合阻害物質を徹底的に除去する必要があ
る。2. Description of the Related Art Many useful polymer compounds are obtained by addition polymerization such as radical polymerization, cationic polymerization, or anionic polymerization of a vinyl compound. However, this reaction is a chain reaction, and therefore, during the production process of the vinyl compound. When a compound having a chain terminating action or a chain transfer action is contained in the above, adverse effects such as a slow polymerization reaction and a decrease in molecular weight occur. Many of these polymerizable inhibitory substances act on the polymerization reaction in an extremely small amount,
Therefore, in order to impart excellent polymerizability to the vinyl compound, it is necessary to thoroughly remove these polymerization inhibitors.
【０００３】またラジカル重合性のビニル化合物には、
製造中、保管中あるいは輸送中などにおける重合を防ぐ
ため、ビニル化合物の製造中や製造後に、しばしば重合
禁止剤が添加される。したがって、ビニル化合物を重合
する際には添加された禁止剤の量を考慮して重合開始剤
を用いることもあるが、高品質の重合体を得るには、ビ
ニル化合物から重合禁止剤を除去した後、重合すること
が望ましい。Further, the radically polymerizable vinyl compound includes
To prevent polymerization during production, storage or transportation, a polymerization inhibitor is often added during or after the production of the vinyl compound. Therefore, when polymerizing a vinyl compound, a polymerization initiator may be used in consideration of the amount of the added inhibitor, but in order to obtain a high quality polymer, the polymerization inhibitor was removed from the vinyl compound. After that, it is desirable to polymerize.
【０００４】酸素原子、窒素原子または硫黄原子を有す
るビニル化合物、すなわち、極性基を有するビニル化合
物（極性ビニル化合物）から、重合禁止剤などを除去す
ることは困難であることが多い。蒸留によって極性ビニ
ル化合物を精製しようとすると、極性ビニル化合物は沸
点や融点が比較的高く、このため一般に減圧下でしかも
融点以上で極性ビニル化合物を留出する必要があり、蒸
留の運転条件が著しく制限される場合がある。さらに蒸
留操作中に極性ビニル化合物が重合してしまうおそれも
あり、工業的に実施するには問題がある。It is often difficult to remove a polymerization inhibitor or the like from a vinyl compound having an oxygen atom, a nitrogen atom or a sulfur atom, that is, a vinyl compound having a polar group (polar vinyl compound). When attempting to purify a polar vinyl compound by distillation, the boiling point and melting point of the polar vinyl compound are relatively high, so it is generally necessary to distill the polar vinyl compound under reduced pressure and above the melting point. There may be restrictions. Further, the polar vinyl compound may be polymerized during the distillation operation, which is a problem for industrial implementation.
【０００５】また極性ビニル化合物を再結晶によって精
製することも行われているが、再結晶溶媒の精製工程や
製品の乾燥工程が必要となり、また、乾燥工程で局部的
な過熱によって極性ビニル化合物のポリマーが生成して
しまうおそれがある。したがって、極性ビニル化合物を
再結晶によって工業的に精製することは、経済的に不利
である。[0005] Further, although a polar vinyl compound is also purified by recrystallization, a purification step of a recrystallization solvent and a drying step of a product are required, and the polar vinyl compound of the polar vinyl compound is locally heated in the drying step. Polymer may be generated. Therefore, it is economically disadvantageous to industrially purify a polar vinyl compound by recrystallization.
【０００６】ビニル化合物特に極性ビニル化合物の溶液
をイオン交換樹脂や活性炭を充填した塔に通して、重合
阻害物質を吸着、除去する方法は、処理液からビニル化
合物を分離する必要がなく、そのまま重合に用いる場合
には有力であり、極性ビニル化合物の精製に広く用いら
れている。しかし、吸着操作に適し、しかも重合反応に
も適した溶媒を入手性、経済性などを考慮にいれて選択
しなければならず、これらの全ての条件を満たす溶媒を
見出すことは実際上不可能であった。さらに、吸着剤の
再生または交換などを行わねばならず、工業規模では煩
わしさがあった。また、遠隔地に輸送する場合、寒冷地
に貯蔵する場合あるいは用途によっては結晶化されたビ
ニル化合物が要求される場合があり、これらの場合には
上記の精製法の場合と同じ問題が生ずることがあった。A method of adsorbing and removing a polymerization inhibitor by passing a solution of a vinyl compound, particularly a polar vinyl compound, through a column packed with an ion exchange resin or activated carbon is not required to separate the vinyl compound from the treatment liquid, and the polymerization is performed as it is. It is effective when used for, and is widely used for purification of polar vinyl compounds. However, a solvent suitable for the adsorption operation and also suitable for the polymerization reaction must be selected in consideration of availability, economical efficiency, etc., and it is practically impossible to find a solvent satisfying all these conditions. Met. Further, the adsorbent must be regenerated or replaced, which is troublesome on an industrial scale. In addition, when transported to remote areas, stored in cold areas, or depending on the application, crystallized vinyl compounds may be required.In these cases, the same problem as in the case of the above-mentioned purification method may occur. was there.
【０００７】一方、特公昭５６−４１２８２号公報に
は、混合物を高圧に加圧することにより一部の成分を析
出せしめ、加圧下において存在する液相と結晶と分離す
る、いわゆる、圧力晶析法が開示されている。このよう
な圧力晶析法は、特開昭６２−２０９０３４号公報、特
開平１−２５０３２９号公報、特開平４−１２００２７
号公報などに開示されているように、キシレン、ナフタ
レン類、クレゾールなどの位置異性体の分離、あるいは
フェノール類のアルキル化反応液からのアルキル化フェ
ノール類の分離などに用いることができることが知られ
ている。しかし、圧力晶析法を、重合性ビニル化合物に
優れた重合性を付与するとの観点から、ビニル化合物の
精製については用いることは開示されていなかった。On the other hand, Japanese Patent Publication No. 56-12882 discloses a so-called pressure crystallization method in which a mixture is pressurized to a high pressure to precipitate a part of the components and the liquid phase and crystals existing under pressure are separated. Is disclosed. Such pressure crystallization method is disclosed in JP-A-62-209034, JP-A-1-250329, and JP-A-4-120027.
It is known that it can be used for separation of positional isomers such as xylene, naphthalene and cresol, or separation of alkylated phenols from an alkylation reaction solution of phenols, as disclosed in Japanese Patent Publication No. ing. However, it has not been disclosed to use the pressure crystallization method for purifying a vinyl compound from the viewpoint of imparting excellent polymerizability to the polymerizable vinyl compound.
【０００８】例えば、N-ビニルカルボン酸アミドは、カ
ルボン酸アミド、アセトアルデヒドおよびアルコールか
らN-(1-アルコキシエチル)カルボン酸アミドを合成し、
これを熱分解または接触分解することによって製造しう
ることが知られている。しかし、N-ビニルカルボン酸ア
ミドと未反応のカルボン酸アミドあるいはN-(1-アルコ
キシエチル)カルボン酸アミドの物性特に沸点や溶解性
が極めて近く、その分離は容易ではなく、これまでいく
つかの方法が提案されている。For example, N-vinylcarboxylic acid amide is prepared by synthesizing N- (1-alkoxyethyl) carboxylic acid amide from carboxylic acid amide, acetaldehyde and alcohol,
It is known that it can be produced by thermal decomposition or catalytic decomposition. However, the physical properties of N-vinylcarboxylic acid amide and unreacted carboxylic acid amide or N- (1-alkoxyethyl) carboxylic acid amide, especially the boiling point and solubility are very close, and their separation is not easy. A method has been proposed.
【０００９】また特開昭６１−２８６０６９号公報に
は、蒸留ではN-ビニルホルムアミドへの未反応原料であ
るホルムアミドの混入は避けられないため、水と芳香族
炭化水素による抽出分離が開示されている。Further, JP-A-61-286069 discloses extraction / separation with water and aromatic hydrocarbons, since mixing of formamide which is an unreacted raw material into N-vinylformamide is unavoidable in distillation. There is.
【００１０】一方、N-ビニルカルボン酸アミドのもう一
つの有力な製造法として、アセトアルデヒドとカルボン
酸アミドからエチリデンビスカルボン酸アミドを合成
し、これをカルボン酸アミドとN-ビニルカルボン酸アミ
ドとに分解することによって得られることが知られてい
る。しかし、このようにしてN-ビニルカルボン酸アミド
を製造しようとすると、物性が類似したカルボン酸アミ
ドとN-ビニルカルボン酸アミドとが等モル生成し、これ
らを分離することは非常に困難となる。そして特開昭６
３−１３２８６８号公報には混合有機溶媒からの冷却晶
析による方法、特開平２−１８８５６０号公報には無機
塩水溶液と芳香族炭化水素を用いた抽出による方法、米
国特許４４０１５１６号明細書には多価アルコールを用
いた抽出蒸留による方法などが開示されている。On the other hand, as another promising method for producing N-vinylcarboxylic acid amide, ethylidene biscarboxylic acid amide is synthesized from acetaldehyde and carboxylic acid amide, and this is converted into carboxylic acid amide and N-vinylcarboxylic acid amide. It is known to be obtained by decomposing. However, when an N-vinylcarboxylic acid amide is produced in this manner, equimolar amounts of a carboxylic acid amide and N-vinylcarboxylic acid amide having similar physical properties are formed, and it is very difficult to separate them. . And JP-A-6
JP-A-3-132868 discloses a method by cooling crystallization from a mixed organic solvent, JP-A-2-188560 discloses a method by extraction with an aqueous solution of an inorganic salt and aromatic hydrocarbon, and US Pat. A method by extractive distillation using a polyhydric alcohol is disclosed.
【００１１】しかし、いずれの場合もこれらの方法で
は、充分な純度のN-ビニルカルボン酸アミドを得ること
は困難である。さらに、抽出法では高価な有機溶媒が必
要であり、これらを回収、精製する設備が必要である。
また、N-ビニルカルボン酸アミドは水に対して比較的不
安定であるため、抽出操作中にN-ビニルカルボン酸アミ
ドの加水分解を引き起こす恐れがあり、工業的に満足の
できる方法ではない。また有機溶媒を用いた冷却晶析に
よる方法は、抽出法と同様に有機溶媒を用いることによ
る問題に加えて、乾燥工程が必要となり、しかもN-ビニ
ルカルボン酸アミドが熱重合する可能性があるという問
題点がある。さらに抽出蒸留法は、有機溶媒を使用する
ため、必要な精留効果を得るには還流比を上げる必要が
あり、このため長時間にわたってN-ビニルカルボン酸ア
ミドを加熱しなければならない。However, in any case, it is difficult to obtain a sufficiently pure N-vinylcarboxylic acid amide by these methods. Furthermore, the extraction method requires an expensive organic solvent and a facility for recovering and purifying these.
Further, since N-vinylcarboxylic acid amide is relatively unstable to water, it may cause hydrolysis of N-vinylcarboxylic acid amide during the extraction operation, which is not an industrially satisfactory method. In addition, the method by cooling crystallization using an organic solvent requires a drying step in addition to the problem caused by using an organic solvent as in the extraction method, and there is a possibility that N-vinylcarboxylic acid amide will be thermally polymerized. There is a problem. Furthermore, since the extractive distillation method uses an organic solvent, it is necessary to increase the reflux ratio in order to obtain the necessary rectification effect, and therefore the N-vinylcarboxylic acid amide must be heated for a long time.
【００１２】このように上述したいずれの方法でも、高
純度で重合性に優れたN-ビニルカルボン酸アミドなどの
極性ビニル化合物を工業的スケールで安定的に効率よく
分離する方法は開示されていない。As described above, none of the above-mentioned methods discloses a method for stably and efficiently separating a polar vinyl compound such as N-vinylcarboxylic acid amide having high purity and excellent polymerizability on an industrial scale. .
【００１３】[0013]
【発明の目的】本発明は、極性基を有するビニル化合物
から重合阻害物質などの不純物を除去することによって
優れた重合性を有するビニル化合物を製造しうるような
極性ビニル化合物の精製方法を提供することを目的とし
ている。It is an object of the present invention to provide a method for purifying a polar vinyl compound which is capable of producing a vinyl compound having excellent polymerizability by removing impurities such as a polymerization inhibitor from the vinyl compound having a polar group. Is intended.
【００１４】[0014]
【発明の概要】本発明によれば、重合阻害物質を含有
し、少なくとも１個の酸素原子、窒素原子または硫黄原
子を有する粗極性ビニル化合物を０〜１００℃で５００
〜３０００気圧に加圧して極性ビニル化合物の結晶を析
出させ、加圧下においてこの結晶を液相から分離するこ
とを特徴とする極性ビニル化合物の精製方法が提供され
る。SUMMARY OF THE INVENTION According to the present invention, a crude polar vinyl compound containing a polymerization inhibitor and having at least one oxygen atom, nitrogen atom or sulfur atom at 0-100 ° C.
A method for purifying a polar vinyl compound is provided, which comprises pressurizing to 3,000 atm to precipitate crystals of the polar vinyl compound, and separating the crystals from the liquid phase under pressure.
【００１５】[0015]
【発明の具体的説明】以下本発明に係る極性ビニル化合
物の精製方法について具体的に説明する。本発明では、
重合阻害物質たとえば重合禁止剤を含有し、少なくとも
１個の酸素原子、窒素原子または硫黄原子を有するビニ
ル化合物（粗極性ビニル化合物）を、圧力晶析法によっ
て処理し、極性ビニル化合物と重合阻害物質とを分離す
ることによって、極性ビニル化合物を精製している。DETAILED DESCRIPTION OF THE INVENTION The method for purifying a polar vinyl compound according to the present invention will be specifically described below. In the present invention,
Polymerization inhibiting substance For example, a vinyl compound containing a polymerization inhibitor and having at least one oxygen atom, nitrogen atom or sulfur atom (crude polar vinyl compound) is treated by a pressure crystallization method to obtain a polar vinyl compound and a polymerization inhibiting substance. The polar vinyl compound is purified by separating and.
【００１６】本発明における晶析圧力は５００〜３００
０気圧であり、特に１０００〜２０００気圧が好まし
い。晶析圧力が５００気圧より低いと、得られる極性ビ
ニル化合物の重合度は大幅には向上せずに１回の晶析操
作によって得られる結晶の量が少なく生産性が低いため
に経済的に不利となる。一方、３０００気圧より高い圧
力で晶析操作を行っても大幅な晶析量の増加は得られ
ず、また得られる極性ビニル化合物の純度が低下し重合
性の向上も小さくなる。また、このような高圧に耐えう
るような装置は大型となり高価である。The crystallization pressure in the present invention is 500 to 300.
It is 0 atm, and particularly preferably 1000 to 2000 atm. When the crystallization pressure is lower than 500 atm, the degree of polymerization of the polar vinyl compound obtained is not significantly improved, and the amount of crystals obtained by one crystallization operation is small, resulting in low productivity, which is economically disadvantageous. Becomes On the other hand, even if the crystallization operation is performed at a pressure higher than 3000 atm, the crystallization amount is not significantly increased, and the purity of the polar vinyl compound obtained is lowered and the improvement of the polymerizability is also reduced. Further, a device that can withstand such a high pressure is large and expensive.
【００１７】一般に、粗極性ビニル化合物の圧力晶析操
作を効率よく行うためには、粗極性ビニル化合物を低温
にすると低い圧力で行うことができるが、高温にすると
高い圧力が必要となる。Generally, in order to carry out the pressure crystallization operation of the crude polar vinyl compound efficiently, it is possible to carry out the crude polar vinyl compound at a low pressure at a low temperature, but it is necessary to perform a high pressure at a high temperature.
【００１８】本発明においては、粗極性ビニル化合物を
予め０〜１００℃好ましくは１０〜７０℃に調整した
後、粗極性ビニル化合物を圧力晶析装置（加圧筒）に導
入する。圧力晶析装置の加圧筒の温度は、粗極性ビニル
化合物を加圧すると断熱圧縮と晶析熱とによってわずか
に上昇するが、この温度上昇を考慮して極性ビニル化合
物の晶析温度を設定するとよい。晶析温度が０℃より低
いと、粗極性ビニル化合物の濃度が高くなりすぎて流動
性が低下し、粗極性ビニル化合物を加圧筒に導入するの
が困難になる。一方粗極性ビニル化合物を１００℃より
高く加熱すると、ビニル化合物の熱重合や変質が起こり
始め、品質や収量低下を引き起こす。In the present invention, the crude polar vinyl compound is previously adjusted to 0 to 100 ° C., preferably 10 to 70 ° C., and then the crude polar vinyl compound is introduced into the pressure crystallizer (pressure cylinder). The temperature of the pressurizing cylinder of the pressure crystallizer slightly rises due to adiabatic compression and heat of crystallization when the crude polar vinyl compound is pressurized, but the crystallization temperature of the polar vinyl compound is set in consideration of this temperature rise. Good to do. When the crystallization temperature is lower than 0 ° C., the concentration of the crude polar vinyl compound becomes too high and the fluidity decreases, and it becomes difficult to introduce the crude polar vinyl compound into the pressure cylinder. On the other hand, when the crude polar vinyl compound is heated above 100 ° C., thermal polymerization or deterioration of the vinyl compound begins to occur, resulting in deterioration of quality and yield.
【００１９】本発明において加圧筒に導入される粗極性
ビニル化合物は、液体であってもよく、また種晶を含む
スラリーであってもよいが、以下の理由から種晶を含む
スラリーが好ましい。すなわち圧力晶析装置の加圧筒に
圧力を加えると、粗極性ビニル化合物は急速に圧力を高
められ、しかも、圧力エネルギーは液相を均一に音速で
伝わる。したがって、加圧筒に供給された粗極性ビニル
化合物中に種晶が含まれていないと、加圧しても極性ビ
ニル化合物は過飽和の状態となり、充分に結晶が生成し
ないことがある。そのため、圧力晶析に先だって粗極性
ビニル化合物を種晶の生成に充分な温度と時間に保って
予め極性ビニル化合物の結晶を生成させておくか、また
は粗極性ビニル化合物の一部を分流させ、これを冷却し
て結晶を生じさせ、この結晶を含んだ粗極性ビニル化合
物と、粗極性ビニル化合物とを混合するか、あるいは外
部から粗極性ビニル化合物に種晶を添加することが望ま
しい。The crude polar vinyl compound introduced into the pressure cylinder in the present invention may be a liquid or a slurry containing seed crystals, but a slurry containing seed crystals is preferred for the following reasons. . That is, when pressure is applied to the pressure cylinder of the pressure crystallizer, the pressure of the crude polar vinyl compound is rapidly increased, and the pressure energy is evenly transmitted through the liquid phase at the speed of sound. Therefore, if seed crystals are not contained in the crude polar vinyl compound supplied to the pressurizing cylinder, the polar vinyl compound may be in a supersaturated state even when pressurized, and crystals may not be sufficiently formed. Therefore, prior to pressure crystallization, the crude polar vinyl compound is kept at a temperature and time sufficient to generate seed crystals to preliminarily generate crystals of the polar vinyl compound, or a part of the crude polar vinyl compound is diverted, It is desirable to cool this to generate crystals, and mix the crude polar vinyl compound containing the crystals with the crude polar vinyl compound, or to add a seed crystal from the outside to the crude polar vinyl compound.
【００２０】一般に圧力晶析では冷却晶析に比べて晶析
速度が大きく、平衡に近い状態に達するまでの時間は短
いが、１回の加圧当たりの晶析量を最大にするため完全
に平衡状態に至るまで加圧状態を保持することが好まし
い。極性ビニル化合物は比較的結晶性が高いので、加圧
状態での保持時間は５分以内好ましくは３分以内であ
る。In general, pressure crystallization has a higher crystallization rate than cooling crystallization, and the time required to reach a state close to equilibrium is short, but the crystallization amount per pressurization is maximized so It is preferable to maintain the pressurized state until the equilibrium state is reached. Since the polar vinyl compound has relatively high crystallinity, the holding time under pressure is within 5 minutes, preferably within 3 minutes.
【００２１】本発明においては、加圧下において固相
（結晶）として析出した極性ビニル化合物と、重合阻害
物質（不純物）が濃縮された液相とを分離することによ
って、優れた重合性を有する高純度の極性ビニル化合物
が得られるが、固相と液相とを分解する際の圧力は１０
００〜２０００気圧が好ましく、晶析圧力よりやや低い
圧力で分離される。この過程で結晶の一部が残存してい
る液相（母液）に溶解、発汗し、極性ビニル化合物の結
晶中に含まれる不純物が母液中に排出されるため、得ら
れる極性ビニル化合物は、一層重合性に優れたものとな
る。In the present invention, by separating the polar vinyl compound deposited as a solid phase (crystal) under pressure from the liquid phase in which the polymerization inhibitor (impurity) is concentrated, it is possible to obtain a high polymer having excellent polymerizability. A polar vinyl compound of high purity is obtained, but the pressure for decomposing the solid phase and the liquid phase is 10
The pressure is preferably 00 to 2000 atm, and the separation is performed at a pressure slightly lower than the crystallization pressure. During this process, some of the crystals are dissolved in the liquid phase (mother liquor) that remains and sweat, and the impurities contained in the crystals of the polar vinyl compound are discharged into the mother liquor. It has excellent polymerizability.
【００２２】本発明で使用される粗極性ビニル化合物
は、少なくとも１個の酸素原子、窒素原子または硫黄原
子を有する極性ビニル化合物と、該ビニル化合物の重合
阻害物質とを含有している。The crude polar vinyl compound used in the present invention contains a polar vinyl compound having at least one oxygen atom, nitrogen atom or sulfur atom, and a polymerization inhibitor for the vinyl compound.
【００２３】上記のような極性ビニル化合物としては、
例えば、次の一般式(1)、(2) 、または(3)の化合物が挙
げられる。 ＣＨ2＝ＣＨＮＲ1ＣＯＲ2 (1) （式中、Ｒ1およびＲ2 はそれぞれ独立に水素原子また
はメチル基を示す。） ＣＨ2＝ＣＲ1ＣＯＯＲ2 (2) （式中、Ｒ1は水素原子、メチル基、またはシアノ基を
示し、Ｒ2は水素原子、アルカリ金属、炭素数１〜５の
アルキル基または水酸基、ジアルキルアミノ基もしくは
第４級アンモニウム基で置換された低級アルキル基を示
す。） ＣＨ2＝ＣＲ1ＣＯＮＲ2Ｒ3 (3) （式中、Ｒ1は水素原子またはメチル基を示し、Ｒ2およ
びＲ3はそれぞれ独立に水素原子、炭素数１〜５のアル
キル基または水酸基、ジアルキルアミノ基、スルフォン
酸基もしくは第４級アンモニウム基で置換された低級ア
ルキル基を示す。） さらに、水酸基、アミノ基などで置換されている芳香族
系ビニル化合物も本発明で使用することができる。As the polar vinyl compound as described above,
For example, the compound of the following general formula (1), (2), or (3) may be mentioned. CH 2 = CHNR 1 COR 2 (1) (In the formula, R 1 and R 2 each independently represent a hydrogen atom or a methyl group.) CH 2 = CR 1 COOR 2 (2) (In the formula, R 1 is hydrogen. An atom, a methyl group or a cyano group is shown, and R 2 is a hydrogen atom, an alkali metal, an alkyl group having 1 to 5 carbon atoms or a lower alkyl group substituted with a hydroxyl group, a dialkylamino group or a quaternary ammonium group. ) CH 2 = CR 1 CONR 2 R 3 (3) (In the formula, R 1 represents a hydrogen atom or a methyl group, and R 2 and R 3 are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a hydroxyl group. , A lower alkyl group substituted with a dialkylamino group, a sulfonic acid group or a quaternary ammonium group.) Furthermore, an aromatic vinyl compound substituted with a hydroxyl group, an amino group or the like may also be used in the present invention. It can be.
【００２４】このような極性ビニル化合物としては、具
体的には、N-ビニルアセトアミド、N-ビニル-N-メチル
アセトアミド、N-ビニルホルムアミド、N-メチル-N-ビ
ニルホルムアミドなどのN-ビニルカルボン酸アミド、N-
メチルアクリルアミド、N-エチルアクリルアミド、N-イ
ソプロピルアクリルアミド、モノメチロールアクリルア
ミド、ジアセトンアクリルアミド、N,N-ジメチルアクリ
ルアミド、N,N-ジエチルアクリルアミド、N,N'-メチレ
ンビスアクリルアミド、2-アクリルアミド-2-メチルプ
ロパンスルホン酸またはそのナトリウム塩、N-メチロー
ルアクリルアミドなどのアクリルアミド、およびメタク
リルアミド誘導体、アクリル酸、メタクリル酸、イタコ
ン酸、ペンタエリスリトールモノアクリレートなどのア
クリル酸エステルおよびメタクリル酸エステル、無水マ
レイン酸、α-シアノアクリル酸エチル、o-,m-,p-ヒド
ロキシスチレン、o-,m-,p-アミノスチレン、n-ビニルカ
ルバゾールなどが挙げられる。Specific examples of such a polar vinyl compound include N-vinylacetamide, N-vinyl-N-methylacetamide, N-vinylformamide, N-methyl-N-vinylformamide and like N-vinylcarboxylic compounds. Acid amide, N-
Methyl acrylamide, N-ethyl acrylamide, N-isopropyl acrylamide, monomethylol acrylamide, diacetone acrylamide, N, N-dimethyl acrylamide, N, N-diethyl acrylamide, N, N'-methylene bis acrylamide, 2-acrylamide-2- Methyl propane sulfonic acid or its sodium salt, acrylamide such as N-methylol acrylamide, and methacrylamide derivative, acrylic acid, methacrylic acid, itaconic acid, acrylic acid ester and methacrylic acid ester such as pentaerythritol monoacrylate, maleic anhydride, α -Ethyl cyanoacrylate, o-, m-, p-hydroxystyrene, o-, m-, p-aminostyrene, n-vinylcarbazole and the like can be mentioned.
【００２５】本発明で使用される粗極性ビニル化合物に
含有される重合阻害物質は、極性ビニル化合物（モノマ
ー）の重合に悪影響を与え、または重合性を阻害する物
質である。このような重合阻害物質としては、ある期間
極性ビニル化合物の重合を全く起こさせない重合禁止剤
（物質）、重合速度を遅らせる重合抑制剤（物質）、分
子量の低下を招く連鎖移動剤（物質）などが挙げられ、
特に制限はない。重合性阻害物質として例示すれば、次
のものが挙げられる。 （１）生長ラジカルと容易に−電子移動反応を行うよう
な金属塩など。The polymerization inhibitor contained in the crude polar vinyl compound used in the present invention is a substance which adversely affects the polymerization of the polar vinyl compound (monomer) or inhibits the polymerizability. As such a polymerization inhibitor, a polymerization inhibitor (substance) that does not cause polymerization of a polar vinyl compound at all for a certain period, a polymerization inhibitor (substance) that delays the polymerization rate, a chain transfer agent (substance) that causes a decrease in molecular weight, etc. ,
There is no particular limitation. Examples of the polymerization inhibitor include the following. (1) Metal salts and the like that easily undergo electron transfer reaction with growing radicals.
【００２６】鉄(III)塩、銅(II)塩など。 （２）１次ラジカルまたは生長ラジカルと容易に連鎖移
動反応をおこし、安定ラジカルを生成する化合物。Iron (III) salts, copper (II) salts and the like. (2) A compound that easily causes a chain transfer reaction with a primary radical or a growing radical to generate a stable radical.
【００２７】ヒドロキノンなどフェノール性水酸基を有
する化合物、芳香族アミン、アリル化合物、ベンジル化
合物など。 （３）１次ラジカルまたは生長ラジカルと容易に付加反
応を起こして安定なラジカルを生成する化合物。Compounds having a phenolic hydroxyl group such as hydroquinone, aromatic amines, allyl compounds and benzyl compounds. (3) A compound that easily undergoes an addition reaction with a primary radical or a growing radical to generate a stable radical.
【００２８】酸素、ベンゾキノン、ニトロソ化合物な
ど。本発明で用いられる粗極性ビニル化合物は、粗極性
ビニル化合物中の極性ビニル化合物の含有率は大きいほ
ど好ましく、４０重量％以上の量で含むことが好まし
く、特に７０重量％以上の量で含むことが好ましい。粗
極性ビニル化合物中に含まれる重合阻害物質以外の成分
としては特に制限はない。粗極性ビニル化合物中の極性
ビニル化合物の含量が４０重量％に満たないと、極性ビ
ニル化合物の回収率が悪く、また、得られる極性ビニル
化合物の重合性が満足できるレベルに達していないこと
が多い。Oxygen, benzoquinone, nitroso compounds and the like. The crude polar vinyl compound used in the present invention is preferably such that the content of the polar vinyl compound in the crude polar vinyl compound is higher, and it is preferably contained in an amount of 40% by weight or more, particularly 70% by weight or more. Is preferred. There are no particular restrictions on the components other than the polymerization inhibitor contained in the crude polar vinyl compound. If the content of the polar vinyl compound in the crude polar vinyl compound is less than 40% by weight, the recovery rate of the polar vinyl compound is poor, and the polymerizability of the obtained polar vinyl compound often does not reach a satisfactory level. .
【００２９】このような粗極性ビニル化合物は、例え
ば、特開昭６１-１０６５４６号公報（エチリデンビス
アセトアミドの熱分解法）、特開昭５０−７６０１５号
公報（２級N-ビニルカルボン酸アミドの製法）などに記
載された方法に得られるが、N-ビニルカルボン酸アミド
の含量が５０重量％以上であれば、これらの方法の熱分
解生成物をそのまま用いても良いし、蒸留操作でN-ビニ
ルカルボン酸アミドを濃縮、あるいは留出してN-ビニル
カルボン酸アミドの含量を上げたものを用いてもよい。
これらの精製操作を行った粗極性ビニル化合物を用いる
と、当然極性ビニル化合物の回収率が向上するし、純
度、重合性も向上するので望ましい。Examples of such a crude polar vinyl compound include those disclosed in JP-A-61-106546 (pyrolysis of ethylidene bisacetamide) and JP-A-50-76015 (secondary N-vinyl carboxylic acid amide). However, if the content of N-vinylcarboxylic acid amide is 50% by weight or more, the thermal decomposition product of these methods may be used as it is, or the N-vinylcarboxylic acid amide may be used by distillation operation. -Vinylcarboxylic acid amide may be concentrated or distilled to increase the content of N-vinylcarboxylic acid amide.
It is desirable to use a crude polar vinyl compound that has been subjected to these purification operations, because the recovery rate of the polar vinyl compound is naturally improved, and the purity and the polymerizability are also improved.
【００３０】極性ビニル化合物としてのN-ビニルカルボ
ン酸アミドは、水に対して不安定であり、空気中の水分
を吸湿して徐々に分解する。特に、酸が存在すると極め
て不安定で加水分解されてしまう。したがって、極性ビ
ニル化合物としてN-ビニルカルボン酸アミドを用いる場
合には、加圧分離装置および原料槽を含めた圧力晶析装
置さらに、製品容器、濾液槽などの付帯設備は、窒素や
乾燥空気などの雰囲気下に保つことが望ましい。またN-
ビニルカルボン酸アミドの加水分解反応を防ぐために、
粗極性ビニル化合物中に少量の硫酸マグネシウムなどの
乾燥剤や重曹などの塩基性物質を添加してもよい。N-vinylcarboxylic acid amide as a polar vinyl compound is unstable to water and absorbs moisture in the air to gradually decompose. In particular, the presence of acid is extremely unstable and causes hydrolysis. Therefore, when N-vinylcarboxylic acid amide is used as the polar vinyl compound, a pressure crystallizer including a pressure separator and a raw material tank, and additional equipment such as a product container and a filtrate tank are used for nitrogen and dry air. It is desirable to keep the atmosphere. Also N-
In order to prevent the hydrolysis reaction of vinylcarboxylic acid amide,
A small amount of a desiccant such as magnesium sulfate or a basic substance such as sodium bicarbonate may be added to the crude polar vinyl compound.
【００３１】上記のようにして粗極性ビニル化合物を圧
力晶析することによって得られる液相には、重合性阻害
物質の他に、ビニル化合物の合成原料、溶媒などが含ま
れているが、ビニル化合物自身もかなり含まれている場
合がある。したがって、この液相をそのまま廃棄しても
よいが、ビニル化合物の反応工程など前工程に回送して
再度用いてもよい。また、この液相からさらに圧力晶
析、冷却晶析または蒸留などの処理でビニル化合物を回
収しても良い。これら２次回収物が充分な重合性を示さ
ない場合には、粗極性ビニル化合物と混合して圧力晶析
工程に戻してもよい。The liquid phase obtained by pressure crystallization of the crude polar vinyl compound as described above contains the raw material for synthesizing the vinyl compound, the solvent, etc. in addition to the polymerizable inhibitor. The compound itself may be contained in a considerable amount. Therefore, although this liquid phase may be discarded as it is, it may be sent to the previous step such as the reaction step of the vinyl compound and used again. Further, the vinyl compound may be recovered from this liquid phase by a treatment such as pressure crystallization, cooling crystallization or distillation. When these secondary recovered materials do not show sufficient polymerizability, they may be mixed with a crude polar vinyl compound and returned to the pressure crystallization step.
【００３２】本発明に係る極性ビニル化合物の精製方法
によって得られる極性ビニル化合物が優れた高重合性を
有する理由は明かでないが、圧力晶析による発汗作用の
他に加圧下の共晶点が冷却晶析の際の共晶点と比べてビ
ニル化合物の晶析に有利であること、比較的低温で短時
間の分離処理を行うため熱によるビニル化合物の劣化が
起こらないこと、得られた結晶が円筒形に固められ表面
積が小さいために吸湿や酸化などによる劣化がされにく
いことなどが考えられる。Although the reason why the polar vinyl compound obtained by the method for purifying a polar vinyl compound according to the present invention has excellent high polymerizability is not clear, in addition to the perspiration effect by pressure crystallization, the eutectic point under pressure is cooled. Compared with the eutectic point at the time of crystallization, it is advantageous for crystallization of vinyl compounds, because the separation treatment at a relatively low temperature for a short time does not cause deterioration of vinyl compounds due to heat, the obtained crystals are Since it is solidified into a cylindrical shape and has a small surface area, it is considered that deterioration due to moisture absorption or oxidation is unlikely.
【００３３】[0033]
【発明の効果】本発明によれば、重合阻害物質を含有す
る粗極性ビニル化合物から高純度で重合性に優れた極性
ビニル化合物を容易に効率よく製造することができる。EFFECTS OF THE INVENTION According to the present invention, a polar vinyl compound having high purity and excellent polymerizability can be easily and efficiently produced from a crude polar vinyl compound containing a polymerization inhibitor.
【００３４】[0034]
【実施例】以下、本発明の実施例と比較例を挙げてさら
に詳しく説明するが、本発明は下記の例によって何ら限
定されるものではない。EXAMPLES The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to the following examples.
【００３５】[0035]
【実施例１】銅含有触媒を用いて、アクリロニトリルの
接触水和によりアクリルアミド含有反応液を得た。この
反応液を常法に従って、アクロニトリルを留去し、濃度
５０重量％のアクリルアミド水溶液を得た。Example 1 An acrylamide-containing reaction liquid was obtained by catalytic hydration of acrylonitrile using a copper-containing catalyst. Acrylonitrile was distilled off from this reaction solution according to a conventional method to obtain an aqueous acrylamide solution having a concentration of 50% by weight.
【００３６】このアクリルアミド水溶液(I)を１０℃ま
で冷却後、圧力晶析容器内で１８００kg／cm2 、１０℃
に保ち、アクリルアミドの結晶を析出させ、これから結
晶を液相（母液）から分離した。このようにして純度９
９.９％のアクリルアミドが得られた。After cooling this acrylamide aqueous solution (I) to 10 ° C., 1800 kg / cm 2 , 10 ° C. in a pressure crystallization vessel.
The crystals were separated from the liquid phase (mother liquor) by precipitating acrylamide crystals. In this way, the purity is 9
9.9% acrylamide was obtained.
【００３７】得られたアクリルアミドの重合性を評価す
るため、水を加えて２０重量％にし、Ｖ−５０（N,N'-
アゾビス-(2-アミジノプロパン）２塩酸塩を６００ppm
加え、４５℃恒温水槽に浸した。１０分後、水で１０重
量％に希釈しＢＬ型粘度計を用いて、３０℃回転数３０
RPMで粘度を測定したところ１２０cpsであった。In order to evaluate the polymerizability of the obtained acrylamide, water was added to make 20% by weight, and V-50 (N, N'-
Azobis- (2-amidinopropane) dihydrochloride 600ppm
In addition, it was immersed in a constant temperature water bath at 45 ° C. After 10 minutes, dilute to 10% by weight with water and use a BL type viscometer to rotate at 30 ° C. 30
When the viscosity was measured by RPM, it was 120 cps.
【００３８】[0038]
【比較例１】実施例１で得られた５０％アクリルアミド
水溶液(I)を５℃に冷却し、晶析したアクリルアミドを
濾別後、４０℃で６時間真空乾燥した。得られたアクリ
ルアミドには銅イオン１０PPM、ポリマーが０.５％含ま
れ、実施例１と同様にして行った重合性評価結果は粘度
が５cpsであった。Comparative Example 1 The 50% acrylamide aqueous solution (I) obtained in Example 1 was cooled to 5 ° C., the crystallized acrylamide was filtered off, and then vacuum dried at 40 ° C. for 6 hours. The obtained acrylamide contained 10 ppm of copper ion and 0.5% of polymer, and the result of polymerizability evaluation conducted in the same manner as in Example 1 was that the viscosity was 5 cps.
【００３９】[0039]
【比較例２】実施例１で得られた５０％アクルアミド水
溶液を強酸性カチオン交換樹脂により脱銅した後、苛性
ソーダで中和し、濃度５０％のアクリルアミド水溶液を
得た。実施例１と同様にして行った重合性評価結果は粘
度が８５cpsであった。Comparative Example 2 The 50% aqueous solution of aculamide obtained in Example 1 was decopperized with a strongly acidic cation exchange resin and then neutralized with caustic soda to obtain an aqueous acrylamide solution having a concentration of 50%. The result of the evaluation of polymerizability carried out in the same manner as in Example 1 was that the viscosity was 85 cps.
【００４０】[0040]
【実施例２】攪拌機、冷却器、温度計付き４つ口フラス
コに５０重量％アクリルアミド水溶液６４０ｇ（４.５
モル）と０.１Ｎ水酸化ナトリウム水溶液１１.７mlを入
れ、３０℃に調整した。このフラスコに水酸化ナトリウ
ムでギ酸を中和した３７重量％ホルムアルデヒドを
（３.８モル）攪拌しながら添加した。４時間後、N-メ
チロールアクリルアミドの生成率は７５％であった。こ
の反応液を０.１Ｎリン酸二水素ナトリウムで中和し
た。Example 2 A four-necked flask equipped with a stirrer, a cooler, and a thermometer was used, and 640 g of a 50 wt% acrylamide aqueous solution (4.5
Mol) and 0.1N aqueous sodium hydroxide solution (11.7 ml) were added and the temperature was adjusted to 30 ° C. To this flask was added 37% by weight formaldehyde (3.8 moles), which was formic acid neutralized with sodium hydroxide, with stirring. After 4 hours, the production rate of N-methylolacrylamide was 75%. The reaction solution was neutralized with 0.1N sodium dihydrogen phosphate.
【００４１】この中和反応液(II)を２０℃に冷却し、圧
力晶析容器内で１８００kg／cm2 、２０℃に保ち、N-メ
チロールアクリルアミドの結晶を析出させ、この結晶を
液相（母液）から分離した。このようにして純度９９.
９％のN-メチロールアクリルアミドが得られた。This neutralization reaction liquid (II) was cooled to 20 ° C. and kept at 1800 kg / cm 2 and 20 ° C. in a pressure crystallization vessel to precipitate N-methylolacrylamide crystals, and these crystals were put into a liquid phase ( Mother liquor). In this way the purity is 99.
9% N-methylolacrylamide was obtained.
【００４２】このN-メチロールアクリルアミドの重合性
を評価するため、水を加えて２０重量％にし、Ｖ−５０
（N,N'-アゾビス-(2-アミジノプロパン）２塩酸塩を６
００ppm加え、４５℃恒温水槽に浸した。１０分後、水
で１０重量％に希釈しＢＬ型粘度計を用いて、３０℃回
転数３０RPMで粘度を測定したところ１５０cpsであっ
た。To evaluate the polymerizability of this N-methylol acrylamide, water was added to make it 20% by weight, and V-50
(N, N'-azobis- (2-amidinopropane) dihydrochloride was added to 6
00 ppm was added and immersed in a constant temperature water bath at 45 ° C. After 10 minutes, the viscosity was 150 cps when diluted with water to 10% by weight and the viscosity was measured using a BL type viscometer at 30 ° C. and 30 RPM.
【００４３】[0043]
【比較例３】実施例２で得られた中和反応液(II)の重合
性を評価するため、水を加えて２０重量％にし、実施例
２と同様にして粘度を測定したところ１０cpsであっ
た。Comparative Example 3 In order to evaluate the polymerizability of the neutralization reaction solution (II) obtained in Example 2, water was added to make it 20% by weight and the viscosity was measured in the same manner as in Example 2 to find that it was 10 cps. there were.
【００４４】[0044]
【実施例３】温度計およびドライアイス−エタノールト
ラップを具備した三つ口フラスコ（２００ml）にアセト
アミド５.９ｇ（０.１モル）、イソプロピルアルコール
４０ｇ（０.６７モル）、エチリデンビスアセトアミド
２.１６ｇ（１５ミリモル）、アセトアルデヒドジイソ
プロピルアセタール１４.６ｇ（０.１モル）を加え、４
５〜４８℃で均一になるまで攪拌、溶解した。濃硫酸
０.４３ｇ（仕込み量に対して０.１重量％）をイソプロ
ピルアルコール２ｇ（３３ミリモル）に溶解（以下の実
施例も同様）した液を加え攪拌後、アセトアルデヒド
１.７６ｇ（０.４モル）を滴下ロートで３分かけて加え
た。滴下終了後５０℃で３時間反応を行い触媒を中和し
た後、ガスクロマトグラフィーで定量したところアセト
アミド転化率８８％、N-(α-プロポキシエチル)アセト
アミドの選択率９４％であり、副生物のエチリデンビス
アセトアミドの選択率５.３％であった。アセタールの
生成量の増減は反応３０分〜３時間の範囲で添加量の１
ミリモル減少し、エチリデンビスアセトアミドは平衡に
なった。得られた反応液から減圧蒸留でN-(α-プロポキ
シエチル)アセトアミドを得、４５０℃、滞留時間１秒
でN-ビニルアセトアミドをイソプロピルアルコールとに
熱分解した。Example 3 In a three-necked flask (200 ml) equipped with a thermometer and a dry ice-ethanol trap, 5.9 g (0.1 mol) of acetamide, 40 g (0.67 mol) of isopropyl alcohol, and ethylidene bisacetamide 2. 16 g (15 mmol) and 14.6 g (0.1 mol) of acetaldehyde diisopropyl acetal were added, and 4
The mixture was stirred and dissolved at 5 to 48 ° C until uniform. A solution prepared by dissolving 0.43 g of concentrated sulfuric acid (0.1% by weight based on the charged amount) in 2 g (33 mmol) of isopropyl alcohol (the same applies to the following examples) was added and stirred, and then 1.76 g of acetaldehyde (0.4%). Mol) was added with a dropping funnel over 3 minutes. After completion of the dropwise addition, the reaction was carried out at 50 ° C for 3 hours to neutralize the catalyst, and then by gas chromatography, the acetamide conversion rate was 88% and the N- (α-propoxyethyl) acetamide selectivity was 94%. The ethylidene bisacetamide selectivity was 5.3%. The amount of acetal produced increases / decreases within the reaction time of 30 minutes to 3 hours by 1
The millimolar decreased and the ethylidene bisacetamide was in equilibrium. N- (α-propoxyethyl) acetamide was obtained from the obtained reaction solution by distillation under reduced pressure, and N-vinylacetamide was thermally decomposed into isopropyl alcohol at 450 ° C. and a residence time of 1 second.
【００４５】このようにして得られた熱分解液(III)を
２０℃に冷却し、圧力晶析容器を用いて１８００kg／cm
2 、２０℃に保ち、N-ビニルアセトアミドの結晶を析出
させ、この結晶を液相（母液）から分離した。純度９
９.９％のN-ビニルアセトアミドが得られた。このN-ビ
ニルアセトアミドの重合性を評価するため、水を加えて
２０重量％にし、Ｖ−５０（N,N'-アゾビス-(2-アミジ
ノプロパン）２塩酸塩を６００ppm加え、４５℃恒温水
槽に浸した。１０分後、水で１０重量％に希釈しＢＬ型
粘度計を用いて、３０℃回転数３０RPMで粘度を測定し
たところ１３０cpsであった。The thermal decomposition liquid (III) thus obtained was cooled to 20 ° C. and 1800 kg / cm 2 using a pressure crystallization vessel.
2 , kept at 20 ° C. to precipitate N-vinylacetamide crystals, which were separated from the liquid phase (mother liquor). Purity 9
9.9% N-vinylacetamide was obtained. In order to evaluate the polymerizability of this N-vinylacetamide, water was added to make it 20% by weight, 600 ppm of V-50 (N, N'-azobis- (2-amidinopropane) dihydrochloride was added, and a constant temperature water bath at 45 ° C was used. After 10 minutes, it was diluted to 10% by weight with water and the viscosity was measured using a BL type viscometer at 30 ° C. and 30 RPM to find 130 cps.
【００４６】[0046]
【比較例４】実施例３で得られた熱分解液(III)を２０
段のオールダーショー型精留装置を用いて還流比２、３
torrで減圧蒸留し、純度９７.５％のN-ビニルアセトア
ミドが得られた。実施例３と同様にしてN-ビニルアセト
アミドの重合性評価試験を行ったところ、粘度は４０cp
sであった。Comparative Example 4 The thermal decomposition liquid (III) obtained in Example 3 was used in 20
Reflux ratio of 2 or 3 using an Oldershaw type rectification unit
Distillation under reduced pressure with torr gave N-vinylacetamide having a purity of 97.5%. When a polymerizability evaluation test of N-vinylacetamide was conducted in the same manner as in Example 3, the viscosity was 40 cp.
It was s.
【００４７】[0047]
【実施例４】N-ビニルアセトアミド８７重量％、N-(α-
メトキシエチル)アセトアミド９重量％、アセトアミド
４重量％からなる混合物(IV)を２０℃に冷却し、圧力晶
析容器内で１８００kg／cm2 、５０℃に保ち、N-ビニル
アセトアミドの結晶を析出させ、この結晶を液相（母
液）から分離した。このようにしてN-(α-メトキシエチ
ル)アセトアミドを６００ppm、アセトアミドを３００pp
m含む純度９９.９％のN-ビニルアセトアミドが回収率５
０％で得られた。Example 4 N-vinylacetamide 87% by weight, N- (α-
A mixture (IV) consisting of 9% by weight of methoxyethyl) acetamide and 4% by weight of acetamide was cooled to 20 ° C. and kept at 1800 kg / cm 2 and 50 ° C. in a pressure crystallization vessel to precipitate N-vinylacetamide crystals. , The crystals were separated from the liquid phase (mother liquor). In this way, 600 ppm of N- (α-methoxyethyl) acetamide and 300 pp of acetamide
Recovery rate of N-vinylacetamide with m purity of 99.9% is 5
Obtained at 0%.
【００４８】このN-ビニルアセトアミドの重合性を評価
するため、水を加えて２０重量％にし、Ｖ−５０（N,N'
-アゾビス-(2-アミジノプロパン）２塩酸塩を６００ppm
加え、４５℃恒温水槽に浸した。１０分後、水で１０重
量％に希釈しＢＬ型粘度計を用いて、３０℃回転数３０
RPMで粘度を測定したところ１５０cpsであった。In order to evaluate the polymerizability of this N-vinylacetamide, water was added to make it 20% by weight, and V-50 (N, N '
-Azobis- (2-amidinopropane) dihydrochloride 600ppm
In addition, it was immersed in a constant temperature water bath at 45 ° C. After 10 minutes, dilute to 10% by weight with water and use a BL type viscometer to rotate at 30 ° C. 30
When the viscosity was measured by RPM, it was 150 cps.
【００４９】[0049]
【比較例５】理論段数２０段を有する５mmスルーザー型
充填材を充填した精留塔に上から１０段目に、実施例４
で用いられたN-ビニルアセトアミドを主成分とする混合
物(IV)を塔底に接続した加熱釜に仕込み、減圧度２mmH
g、還流比３で精留を行った。塔頂からN-(α-メトキシ
エチル)アセトアミドを７重量％、アセトアミドを４重
量％含む純度８９％のN-ビニルアセトアミドが得られ
た。[Comparative Example 5] A rectification column packed with a 5 mm sulzer type packing material having 20 theoretical plates was used in Example 4 at the 10th plate from the top.
The mixture (IV) containing N-vinylacetamide as the main component used in 1. was charged into a heating pot connected to the bottom of the column, and the degree of vacuum was 2 mmH.
The rectification was carried out at a reflux ratio of 3 g. From the column top, N-vinylacetamide containing 7% by weight of N- (α-methoxyethyl) acetamide and 4% by weight of acetamide and having a purity of 89% was obtained.
【００５０】得られた留分について実施例４と同様にし
て重合性評価試験を行ったところ、粘度は５０cpsであ
った。A polymerization evaluation test was conducted on the obtained fraction in the same manner as in Example 4. The viscosity was 50 cps.
【００５１】[0051]
【実施例５】プロピレンの気相酸化反応で合成されたア
クリル酸に、水による吸収工程、水溶液の酢酸ブチルに
よる抽出工程、共沸蒸留工程、精留工程を加えて得られ
た粗アクリル酸(V)には、アクロレイン５００ppb、酢酸
２０００ppm 、ベンズアルデヒド１５００ppb、フルフ
リルアルデヒド７００ppb、プロピオン酸４００ppm、ア
クリル酸ダイマー２０００ppmが含まれていた。Example 5 A crude acrylic acid obtained by adding an absorption step with water, an extraction step with an aqueous solution of butyl acetate, an azeotropic distillation step, and a rectification step to acrylic acid synthesized by a gas phase oxidation reaction of propylene ( V) contained acrolein 500 ppb, acetic acid 2000 ppm, benzaldehyde 1500 ppb, furfuryl aldehyde 700 ppb, propionic acid 400 ppm, and acrylic acid dimer 2000 ppm.
【００５２】この粗アクリル酸を１５℃に冷却し、圧力
晶析容器内で１８００kg／cm2 、１８℃に保ち、アクリ
ル酸の結晶を析出させ、この結晶を液相（母液）から分
離したところ、純度９９.９％のアクリル酸が回収率７
５％で得られた。このアクリル酸には、アクロレイン１
０ppb 、酢酸２５ppm、ベンズアルデヒド１１０ppb、フ
ルフリルアルデヒド５ppb、プロピオン酸３０ppm、アク
リル酸ダイマー１５ppmが含まれていた。The crude acrylic acid was cooled to 15 ° C. and kept at 1800 kg / cm 2 and 18 ° C. in a pressure crystallization vessel to precipitate crystals of acrylic acid, and the crystals were separated from the liquid phase (mother liquor). , 99.9% pure acrylic acid has a recovery rate of 7
Obtained at 5%. This acrylic acid has acrolein 1
It contained 0 ppb, acetic acid 25 ppm, benzaldehyde 110 ppb, furfuryl aldehyde 5 ppb, propionic acid 30 ppm, and acrylic acid dimer 15 ppm.
【００５３】このアクリル酸の重合性を評価するため、
試験管中で水を加えて２０重量％にし、Ｖ−５０（N,N'
-アゾビス-(2-アミジノプロパン）２塩酸塩を２重量％
加え、４５℃恒温水槽に浸した。１０分後、アクリル酸
水溶液の温度は４６.５℃に上昇した。To evaluate the polymerizability of this acrylic acid,
Add water to 20% by weight in a test tube and add V-50 (N, N '
-Azobis- (2-amidinopropane) dihydrochloride 2% by weight
In addition, it was immersed in a constant temperature water bath at 45 ° C. After 10 minutes, the temperature of the acrylic acid aqueous solution rose to 46.5 ° C.
【００５４】[0054]
【比較例６】実施例５で得られた粗アクリル酸(V)を４m
mHg、６０℃で減圧蒸留を行った。この蒸留アクリル酸
にはアクロレイン３００ppb、酢酸６００ppm、ベンズア
ルデヒド４００ppb、フルフリルアルデヒド５００ppb、
プロピオン酸３００ppm、アクリル酸ダイマー１５０ppm
が含まれていた。このようにして蒸留によって精製され
たアクリル酸に対して、実施例５と同様にして重合性の
評価を行ったところ、４５℃恒温水槽に浸してから１５
分経過してもアクリル酸水溶液の温度は４６℃に上がら
なかった。Comparative Example 6 The crude acrylic acid (V) obtained in Example 5 was added to 4 m.
Vacuum distillation was performed at mHg and 60 ° C. For this distilled acrylic acid, acrolein 300 ppb, acetic acid 600 ppm, benzaldehyde 400 ppb, furfuryl aldehyde 500 ppb,
Propionic acid 300ppm, acrylic acid dimer 150ppm
Was included. The acrylic acid purified by distillation in this way was evaluated for polymerizability in the same manner as in Example 5, and after being immersed in a constant temperature water bath at 45 ° C., 15
The temperature of the acrylic acid aqueous solution did not rise to 46 ° C. even after a lapse of minutes.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ０７Ｃ 233/27 233/38 255/23 309/69 (72)発明者 中 村 仁 至 大分県大分市大字中の洲２ 昭和電工株式 会社大分研究所内 (72)発明者 ト 部 克 文 兵庫県神戸市中央区脇浜町１丁目３番18号 株式会社神戸製鋼所神戸本社内 (72)発明者 吉 田 紳 吾 兵庫県神戸市中央区脇浜町１丁目３番18号 株式会社神戸製鋼所神戸本社内─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification code Internal reference number FI Technical display location C07C 233/27 233/38 255/23 309/69 (72) Inventor Hitoshi Nakamura To Oita prefecture Oita 2 Nakanosu, City of Oita, Showa Denko Co., Ltd. (72) Inventor Katsufumi Tobe 1-3-18 Wakihamacho, Chuo-ku, Kobe-shi, Hyogo Kobe Steel Works, Ltd. Kobe Head Office (72) Inventor Yoshi Shingo Ta, 1-3-18 Wakihama-cho, Chuo-ku, Kobe-shi, Hyogo Prefecture Kobe Steel, Ltd. Kobe Head Office
Claims (4)
の酸素原子、窒素原子または硫黄原子を有する粗極性ビ
ニル化合物を、０〜１００℃で５００〜３０００気圧に
加圧して極性ビニル化合物の結晶を析出せしめ、加圧下
において極性ビニル化合物の結晶と液相とを分離して高
純度の極性ビニル化合物を得ることを特徴とする極性ビ
ニル化合物の精製方法。1. A crystal of a polar vinyl compound containing a polymerization inhibitor and pressurizing a crude polar vinyl compound having at least one oxygen atom, nitrogen atom or sulfur atom to 500 to 3000 atm at 0 to 100 ° C. And a crystal of the polar vinyl compound and a liquid phase are separated under pressure to obtain a highly pure polar vinyl compound.
る化合物であることを特徴とする請求項１の精製方法。 ＣＨ2＝ＣＨＮＲ1ＣＯＲ2 (1) （式中、Ｒ1およびＲ2 はそれぞれ独立に水素原子また
はメチル基を示す。）2. The purification method according to claim 1, wherein the polar vinyl compound is a compound represented by the general formula (1). CH 2 = CHNR 1 COR 2 (1) (In the formula, R 1 and R 2 each independently represent a hydrogen atom or a methyl group.)
る化合物であることを特徴とする請求項１の精製方法。 ＣＨ2＝ＣＲ1ＣＯＯＲ2 (2) （式中、Ｒ1は水素原子、メチル基、またはシアノ基を
示し、Ｒ2は水素原子、アルカリ金属、炭素数１〜５の
アルキル基または水酸基、ジアルキルアミノ基もしくは
第４級アンモニウム基で置換された低級アルキル基を示
す。）3. The purification method according to claim 1, wherein the polar vinyl compound is a compound represented by the general formula (2). CH 2 = CR 1 COOR 2 (2) (In the formula, R 1 represents a hydrogen atom, a methyl group, or a cyano group, and R 2 represents a hydrogen atom, an alkali metal, an alkyl group having 1 to 5 carbon atoms, a hydroxyl group, or a dialkyl group. (A lower alkyl group substituted with an amino group or a quaternary ammonium group is shown.)
る化合物であることを特徴とする請求項１の精製方法。 ＣＨ2＝ＣＲ1ＣＯＮＲ2Ｒ3 (3) （式中、Ｒ1は水素原子またはメチル基を示し、Ｒ2およ
びＲ3はそれぞれ独立に水素原子、炭素数１〜５のアル
キル基または水酸基、ジアルキルアミノ基、スルフォン
酸基もしくは第４級アンモニウム基で置換された低級ア
ルキル基を示す。）4. The purification method according to claim 1, wherein the polar vinyl compound is a compound represented by the general formula (3). CH 2 = CR 1 CONR 2 R 3 (3) (In the formula, R 1 represents a hydrogen atom or a methyl group, R 2 and R 3 are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a hydroxyl group, A lower alkyl group substituted with a dialkylamino group, a sulfonic acid group or a quaternary ammonium group is shown.)
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23501193A JP2619202B2 (en) | 1993-09-21 | 1993-09-21 | Purification method of polar vinyl compound |
| US08/305,962 US5510515A (en) | 1993-09-21 | 1994-09-16 | Process for purifying polar vinyl compound |
| EP94114716A EP0644180B1 (en) | 1993-09-21 | 1994-09-19 | Process for purifying polar vinyl compounds |
| DE1994610197 DE69410197T2 (en) | 1993-09-21 | 1994-09-19 | Process for cleaning polar vinyl compounds |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23501193A JP2619202B2 (en) | 1993-09-21 | 1993-09-21 | Purification method of polar vinyl compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0789915A true JPH0789915A (en) | 1995-04-04 |
| JP2619202B2 JP2619202B2 (en) | 1997-06-11 |
Family
ID=16979750
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP23501193A Expired - Fee Related JP2619202B2 (en) | 1993-09-21 | 1993-09-21 | Purification method of polar vinyl compound |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP2619202B2 (en) |
| DE (1) | DE69410197T2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0881428A (en) * | 1994-07-14 | 1996-03-26 | Showa Denko Kk | Highly polymerizable n-vinylcarboxamide and its production |
| WO1999006348A1 (en) * | 1997-07-30 | 1999-02-11 | Mitsubishi Rayon Co., Ltd. | Process for the purification of (meth)acrylic acid |
| JP2007070356A (en) * | 2005-08-11 | 2007-03-22 | Showa Denko Kk | Production method of high-purity n-vinylcarboxylic acid amide |
| JP2008521849A (en) | 2004-12-01 | 2008-06-26 | ビーエーエスエフ ソシエタス・ヨーロピア | Purification of polar vinyl compounds |
| JP2011012068A (en) * | 2010-08-13 | 2011-01-20 | Arkema Inc | Metal surface which suppresses polymerization of ethylenically unsaturated monomer |
-
1993
- 1993-09-21 JP JP23501193A patent/JP2619202B2/en not_active Expired - Fee Related
-
1994
- 1994-09-19 DE DE1994610197 patent/DE69410197T2/en not_active Expired - Lifetime
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0881428A (en) * | 1994-07-14 | 1996-03-26 | Showa Denko Kk | Highly polymerizable n-vinylcarboxamide and its production |
| WO1999006348A1 (en) * | 1997-07-30 | 1999-02-11 | Mitsubishi Rayon Co., Ltd. | Process for the purification of (meth)acrylic acid |
| US6380427B1 (en) | 1997-07-30 | 2002-04-30 | Mitsubishi Rayon Co., Ltd. | Process for purification of (meth)acrylic acid |
| JP2008521849A (en) | 2004-12-01 | 2008-06-26 | ビーエーエスエフ ソシエタス・ヨーロピア | Purification of polar vinyl compounds |
| JP2007070356A (en) * | 2005-08-11 | 2007-03-22 | Showa Denko Kk | Production method of high-purity n-vinylcarboxylic acid amide |
| JP2011012068A (en) * | 2010-08-13 | 2011-01-20 | Arkema Inc | Metal surface which suppresses polymerization of ethylenically unsaturated monomer |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2619202B2 (en) | 1997-06-11 |
| DE69410197D1 (en) | 1998-06-18 |
| DE69410197T2 (en) | 1999-01-21 |
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