JPH0551362A - Method for purifying self-polymerizable monomer - Google Patents

Abstract

PURPOSE:To purify a self-polymerizable monomer to high purity under mild conditions with excellent productivity by removing impurities from the crude self-polymerizable monomer with a specific solvent. CONSTITUTION:A crude self-polymerizable monomer is dissolved in a nonaqueous solvent which is an organic halogenated hydrocarbon-based solvent (e.g. methylene chloride or chloroform). Another kind of nonaqueous solvent, e.g. an aliphatic saturated hydrocarbon-based solvent (e.g. pentane or hexane), compatible with the above-mentioned nonaqueous solvent and capable of selectively precipitating organic impurities dissolved in the nonaqueous solvent and a salt are added to the resultant solution. Water is subsequently mixed to extract and remove the impurities into the water. The formed precipitates and an organic layer are separated from the aqueous layer to recover the self- polymerizable monomer useful as a precursor for polymer compounds from the organic layer.

Description

【発明の詳細な説明】Detailed Description of the Invention

【０００１】[0001]

【産業上の利用分野】本発明は、高分子化合物の前駆体
である自己重合性モノマーの精製法に関する。TECHNICAL FIELD The present invention relates to a method for purifying a self-polymerizable monomer which is a precursor of a polymer compound.

【０００２】[0002]

【従来の技術】有機化合物の精製には蒸留、再結晶、昇
華、再沈等多種多様な方法が古来より知られており産業
上の広い分野に用いられている。高分子化学の分野にお
いてもプラスチック類が産業上の先端的な分野に用いら
れるようになるにつれてその高純度化が強く求められる
ようになっている。例えば、半導体関連製品には無機イ
オン類の低減が、また光学関連製品には光線透過性を阻
害する副生成物の低減が必要とされている。しかし高分
子化合物自体の精製は沸点や溶解性等の点で困難である
場合が多く、そのために高分子化合物の前駆体であるモ
ノマーを精製し、しかる後に重合反応を経て高純度の高
分子化合物を得るという方法が多く用いられている。2. Description of the Related Art Various methods such as distillation, recrystallization, sublimation and reprecipitation have been known for a long time for purification of organic compounds and have been used in a wide range of industrial fields. Also in the field of polymer chemistry, as plastics are used in the most advanced fields of industry, there is a strong demand for high purity. For example, semiconductor-related products require reduction of inorganic ions, and optical-related products require reduction of by-products that impair light transmittance. However, purification of the polymer compound itself is often difficult in terms of boiling point, solubility, etc. Therefore, the monomer that is the precursor of the polymer compound is purified, and then a high-purity polymer compound is obtained through a polymerization reaction. Is often used.

【０００３】一方、高分子化合物のモノマーは一般的に
熱、光、触媒等によって重合反応を起こしやすく、前述
の各種精製法の中で実際にこれら自己重合性モノマーに
適用できるものは限定される。これら自己重合性モノマ
ー、特に下記式Ｉによって示されるマレイミド系化合物
に関しては再結晶、再沈等のほか、種々の方法が公知で
ある。On the other hand, a polymer compound monomer generally tends to undergo a polymerization reaction by heat, light, a catalyst, etc., and there are limits to what can be actually applied to these self-polymerizable monomers in the above-mentioned various purification methods. .. With respect to these self-polymerizable monomers, particularly maleimide compounds represented by the following formula I, various methods are known in addition to recrystallization and reprecipitation.

【化２】 （ＲはＣ、Ｈ、Ｎ、Ｏ、Ｓのうちのいずれかの元素の組
み合わせによって構成される脂肪族又は芳香族の基を示
し、ｎは１以上の整数を示す。）[Chemical 2] (R represents an aliphatic or aromatic group composed of a combination of any one of C, H, N, O, and S, and n represents an integer of 1 or more.)

【０００４】例えば、特開昭６０−１００５５４号公報
にはイソプロパノールを用いた再結晶法が、また特開昭
５６−１０４８６５号公報にはメタノールを添加した後
再沈を行う方法が、また特開昭６２−２３８２６２号公
報には超臨界液体による抽出法が示されている。For example, JP-A-60-100554 discloses a recrystallization method using isopropanol, and JP-A-56-104865 discloses a method of reprecipitation after adding methanol. Japanese Unexamined Patent Publication No. 62-238262 discloses an extraction method using a supercritical fluid.

【０００５】しかしながら、再結晶法は本質的に歩留り
の低下が不可避であり、また再沈法は精製効果が十分と
は言い難い。また超臨界液体による抽出や膜分離等の先
端的な手法は設備投資に関わる問題点が多く、コストや
プラントスケール上の制約が多い。However, the recrystallization method is essentially unavoidable in yield reduction, and the reprecipitation method cannot be said to have a sufficient refining effect. Further, advanced methods such as extraction with supercritical liquid and membrane separation have many problems related to capital investment, and there are many restrictions on cost and plant scale.

【０００６】[0006]

【発明が解決しようとする課題】本発明は、自己重合性
モノマーの粗製物を温和で生産性の高い方法により高純
度に精製する方法を提供することを目的とする。SUMMARY OF THE INVENTION It is an object of the present invention to provide a method for purifying a crude product of a self-polymerizing monomer to a high purity by a mild and highly productive method.

【０００７】[0007]

【課題を解決するための手段】本発明者らは上記の問題
を解決するに当たり鋭意検討した結果、自己重合性モノ
マー粗製物を非水系溶剤〔１〕、非水系溶剤〔１〕と相
溶し、かつ非水系溶剤〔１〕中に溶解している有機性不
純物を選択的に沈澱させる別種の非水系溶剤〔２〕及び
特定の塩〔３〕と水を用いて自己重合性モノマーを生産
性の高い方法により高純度に精製できることを見出し、
この知見に基づいて本発明を完成するに至った。Means for Solving the Problems As a result of intensive studies for solving the above problems, the present inventors have found that a crude self-polymerizable monomer is compatible with a non-aqueous solvent [1] and a non-aqueous solvent [1]. And a non-aqueous solvent [1] that selectively precipitates organic impurities dissolved in the non-aqueous solvent [1], and a specific salt [3] and water are used to produce a self-polymerizable monomer. Found that it can be purified to high purity by a high
The present invention has been completed based on this finding.

【０００８】すなわち、本発明は自己重合性モノマー粗
製物を非水系溶剤〔１〕に溶解し、次いで得られた溶液
に、非水系溶剤〔１〕と相溶し、かつ非水系溶剤〔１〕
中に溶解している有機性不純物を選択的に沈澱させる別
種の非水系溶剤〔２〕並びにアルカリ金属塩、アルカリ
土類金属塩及びアンモニウム塩から選ばれる塩〔３〕を
添加し、次いで水を混合して不純物を水中に抽出除去し
た後、生成した沈殿と有機層と水層とを分離し、有機層
から自己重合性モノマーを回収することを特徴とする自
己重合性モノマーの精製法を提供するものである。That is, in the present invention, the crude self-polymerizable monomer is dissolved in the non-aqueous solvent [1], and then the resulting solution is compatible with the non-aqueous solvent [1] and the non-aqueous solvent [1].
Another non-aqueous solvent [2] that selectively precipitates the organic impurities dissolved therein and a salt [3] selected from alkali metal salts, alkaline earth metal salts and ammonium salts are added, and then water is added. A method for purifying a self-polymerizable monomer, characterized in that after mixing and extracting and removing impurities into water, the generated precipitate is separated from the organic layer and the aqueous layer, and the self-polymerizable monomer is recovered from the organic layer. To do.

【０００９】自己重合性モノマー粗製物中には、その原
材料や触媒等反応試剤の残渣や自己重合物、副生成物等
有機、無機を問わず多種多様な不純物が含まれている。
これらをすべて除去するためには公知な精製法を多段階
に組み合わせる必要があり、工業材料として生産性の点
で困難を極める。しかるに本発明によれば、非水系溶剤
〔１〕中に溶解した無機性不純物及び水に溶解し得る有
機性不純物は早やかに混合した水により抽出され、一方
水に不溶の有機性不純物も同時に非水系溶剤〔２〕の作
用により沈澱を生じる。したがって、結果として有機層
の溶液中には不純物を除去された自己重合性モノマーの
みが存在し、これを濾過、エバポレーション等で溶剤と
分離することにより、高純度の自己重合性モノマーを得
ることができる。A crude product of a self-polymerizable monomer contains a wide variety of impurities such as raw materials, residues of reaction reagents such as catalysts, self-polymerized products, by-products such as organic and inorganic substances.
In order to remove all of them, it is necessary to combine known purification methods in multiple stages, which is extremely difficult in terms of productivity as an industrial material. However, according to the present invention, the inorganic impurities and the water-soluble organic impurities dissolved in the non-aqueous solvent [1] are rapidly extracted with water, while the water-insoluble organic impurities are also extracted. At the same time, precipitation occurs due to the action of the non-aqueous solvent [2]. Therefore, as a result, only the self-polymerizable monomer from which impurities have been removed is present in the solution of the organic layer, and a high-purity self-polymerizable monomer is obtained by separating this from the solvent by filtration, evaporation, etc. You can

【００１０】本発明に用いられる非水系溶剤〔１〕は、
自己重合性モノマーを十分に溶解するとともに非水系溶
剤〔２〕と完全に相溶する必要があり、この要求を満た
すものとして有機ハロゲン化炭化水素系溶剤が好まし
い。具体的には塩化メチレン、クロロホルム、四塩化炭
素、ジクロルエチレン、トリクロルエチレン、ジクロル
エタン、トリクロルエタン、テトラクロルエチレン、テ
トラクロルエタン、クロルベンゼン等が用いられる。ま
た、非水系溶剤〔２〕としては、非水系溶剤〔１〕中に
溶解している有機性不純物を選択的に沈澱させる必要か
ら脂肪族飽和炭化水素系溶剤が好ましい。具体的にはペ
ンタン、ヘキサン、シクロヘキサン、ヘプタン、オクタ
ン、イソオクタン、デカン、石油エーテル等が好まし
い。The non-aqueous solvent [1] used in the present invention is
It is necessary that the self-polymerizable monomer is sufficiently dissolved and completely compatible with the non-aqueous solvent [2], and an organic halogenated hydrocarbon solvent is preferable as one satisfying this requirement. Specifically, methylene chloride, chloroform, carbon tetrachloride, dichloroethylene, trichloroethylene, dichloroethane, trichloroethane, tetrachloroethylene, tetrachloroethane, chlorobenzene and the like are used. The non-aqueous solvent [2] is preferably an aliphatic saturated hydrocarbon solvent because it is necessary to selectively precipitate the organic impurities dissolved in the non-aqueous solvent [1]. Specifically, pentane, hexane, cyclohexane, heptane, octane, isooctane, decane, petroleum ether and the like are preferable.

【００１１】また、非水系溶剤〔２〕とともに用いる特
定の塩〔３〕は上記の無機物及び水溶性有機物の抽出、
並びに非水系溶剤〔２〕による有機性不純物の沈澱を促
進させる効果を有しており、また同時に混合した水と有
機層の分離を促進する効果をも有している。前者の効果
は所謂塩析に属するものであるが、非水系溶剤〔２〕と
ともに用いられることにより有機、無機すべての不純物
の除去に有効である。。塩〔３〕としてはほとんどすべ
てのアルカリ金属塩、アルカリ土類金属塩、アンモニウ
ム塩等が用いることができるが、特に炭酸塩、炭酸水素
塩、酢酸塩、シュウ酸塩が好ましい。Further, the specific salt [3] used together with the non-aqueous solvent [2] is extracted with the above-mentioned inorganic substances and water-soluble organic substances,
It also has the effect of promoting the precipitation of organic impurities by the non-aqueous solvent [2], and at the same time has the effect of promoting the separation of the mixed water and organic layer. The former effect belongs to so-called salting-out, but it is effective in removing all organic and inorganic impurities when used together with the non-aqueous solvent [2]. .. As the salt [3], almost all alkali metal salts, alkaline earth metal salts, ammonium salts and the like can be used, but carbonates, hydrogen carbonates, acetates and oxalates are particularly preferable.

【００１２】一方、精製を行う自己重合性モノマーとし
ては、基本的には非水系溶剤〔１〕に十分な溶解度を有
し、それ自体が非水溶性であればあらゆる有機物が適用
できるが、特に反応性が高く熱や酸、アルカリ等の苛酷
な条件下での取り扱いが困難なもの、具体的にはスチレ
ン誘導体、アクリル基又はメタクリル基含有物質、α，
β−不飽和結合含有物質、エポキシ樹脂原料モノマー等
が適している。中でも電気、電子材料用途に多く用いら
れることから高純度を求められ、かつオリゴマーを生成
しやすい下記式Ｉで示されるマレイミド化合物が本発明
の精製法の最も有効な対象である。On the other hand, as the self-polymerizing monomer to be purified, basically any organic substance can be used as long as it has sufficient solubility in the non-aqueous solvent [1] and is itself insoluble in water. A substance that has high reactivity and is difficult to handle under severe conditions such as heat, acid, and alkali, specifically, a styrene derivative, a substance containing an acrylic group or a methacrylic group, α,
A β-unsaturated bond-containing substance, an epoxy resin raw material monomer and the like are suitable. Among them, the maleimide compound represented by the following formula I, which is required to have high purity because it is often used for electric and electronic materials and is easy to form an oligomer, is the most effective target of the purification method of the present invention.

【００１３】[0013]

【化３】 （ＲはＣ、Ｈ、Ｎ、Ｏ、Ｓのうちのいずれかの元素の組
み合わせによって構成される脂肪族又は芳香族の基を示
し、ｎは１以上の整数を示す。）[Chemical 3] (R represents an aliphatic or aromatic group composed of a combination of any one of C, H, N, O, and S, and n represents an integer of 1 or more.)

【００１４】本発明は、具体的には、下記式で表わされ
る化合物に好適に適用される。The present invention is suitably applied to the compounds represented by the following formulas.

【００１５】[0015]

【化４】 [Chemical 4]

【００１６】また、非水系溶剤〔１〕に対する非水系溶
剤〔２〕及び塩〔３〕の添加量は、用いる自己重合性モ
ノマーの種類や溶剤の種類により異なるが、重量非で
〔１〕／〔２〕＝９５／５〜７０／３０、好ましくは９
０／１０〜８０／２０が、また〔１〕／〔３〕＝９９．
９９／０．０１〜９９．９０／０．１０が適切であ
る）。The addition amount of the non-aqueous solvent [2] and the salt [3] to the non-aqueous solvent [1] varies depending on the kind of the self-polymerizable monomer used and the kind of the solvent. [2] = 95/5 to 70/30, preferably 9
0/10 to 80/20, and [1] / [3] = 99.
99 / 0.01 to 99.90 / 0.10 are suitable).

【００１７】[0017]

【実施例】以下、本発明を実施例に基づいて詳細に説明
する。ただし、本発明は以下の実施例のみに限定される
ものではない。 実施例１ 無水マレイン酸９８ｇをアセトン１ｋｇ中に溶解し、こ
れとは別にアリルアミン５７ｇをアセトン５００ｇ中に
溶解した。アリルアミン溶液を無水マレイン酸溶液中へ
少量ずつ滴下し、２０時間室温で反応させた。次いで、
無水酢酸１２２ｇ及び酢酸カリウム９．８ｇを加え、更
に２０時間４０℃で反応させた。この溶液を２０ｋｇの
水中に投入し、析出した固体を濾過して集め、Ｎ−アリ
ルマレイミドの粗製物を得た。EXAMPLES The present invention will be described in detail below based on examples. However, the present invention is not limited to the following examples. Example 1 98 g of maleic anhydride was dissolved in 1 kg of acetone, and separately, 57 g of allylamine was dissolved in 500 g of acetone. The allylamine solution was dropped little by little into the maleic anhydride solution, and the mixture was reacted for 20 hours at room temperature. Then
122 g of acetic anhydride and 9.8 g of potassium acetate were added, and the mixture was further reacted at 40 ° C. for 20 hours. This solution was put into 20 kg of water, and the precipitated solid was collected by filtration to obtain a crude product of N-allylmaleimide.

【００１８】この粗製物をクロロホルム８００ｇ中に加
え溶解させ、次いでｎ−ヘキサン２００ｇ及び炭酸ナト
リウム０．１ｇを加えて激しく撹拌し粗製物を溶解さ
せ、次いでイオン交換水３５０ｇを加え、更に激しく撹
拌した。撹拌を停止して数分後、水層（上層）と有機層
（下層）が分離し、同時に黒色のタール状物質が沈澱し
た。分液ロートを用いて水層と沈澱を分離して均一な有
機層を単離し、ロータノーエバポレーターを用いて溶剤
を減圧留去し乾燥した。ゲルパーミエーションクロマト
グラフィーを用いて分析した結果、精製によりオリゴマ
ー及び低分子の不純物が減少したことを確認した。ま
た、無機性不純物量の指標となる抽出液電導度を測定し
た結果からも精製の効果を確認した（表１）。This crude product was added to 800 g of chloroform and dissolved, then 200 g of n-hexane and 0.1 g of sodium carbonate were added and vigorously stirred to dissolve the crude product, 350 g of ion-exchanged water was added, and further vigorously stirred. .. A few minutes after the stirring was stopped, the aqueous layer (upper layer) and the organic layer (lower layer) were separated, and at the same time, a black tar-like substance was precipitated. The aqueous layer and the precipitate were separated using a separating funnel to isolate a uniform organic layer, and the solvent was distilled off under reduced pressure using a Rotano evaporator. As a result of analysis using gel permeation chromatography, it was confirmed that the oligomer and low-molecular impurities were reduced by the purification. The effect of purification was also confirmed from the results of measuring the conductivity of the extract, which is an index of the amount of inorganic impurities (Table 1).

【００１９】実施例２ 実施例１で用いたアリルアミンに代えて４，４′−ジア
ミノジフェニルメタン９９ｇを用いて、同様にビス（４
−マレイミドフェニル）メタン粗製物を合成した。ま
た、実施例１と同様に精製を行い、同精製物を得た。ゲ
ルパーミエーションクロマトグラフィー及び抽出液電導
度の分析により精製の効果を確認した（表１）。Example 2 99 g of 4,4'-diaminodiphenylmethane was used in place of the allylamine used in Example 1, and bis (4
-Maleimidophenyl) methane crude was synthesized. Further, purification was carried out in the same manner as in Example 1 to obtain the same purified product. The effect of purification was confirmed by gel permeation chromatography and analysis of the conductivity of the extract (Table 1).

【００２０】実施例３ 実施例１で用いたアリルアミンに代えて２，２−ビス
〔４−（４−アミノフェノキシ）フェニル〕プロパン２
０５ｇを用いて、同様に２，２−ビス〔４−（４−マレ
イミドフェノキシ）フェニル〕プロパン粗製物を合成し
た。また、実施例１と同様に精製を行い、同精製物を得
た。ゲルパーミエーションクロマトグラフィー及び抽出
液電導度の分析により精製の効果を確認した（表１）。Example 3 2,2-bis [4- (4-aminophenoxy) phenyl] propane 2 in place of the allylamine used in Example 1
Crude 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane was similarly synthesized using 05 g. Further, purification was carried out in the same manner as in Example 1 to obtain the same purified product. The effect of purification was confirmed by gel permeation chromatography and analysis of the conductivity of the extract (Table 1).

【００２１】実施例４ 実施例１において用いたクロロホルムを塩化メチレンに
替えて、同様にＮ−アリルマレイミドの合成及び精製を
行った。Example 4 Chloroform used in Example 1 was replaced with methylene chloride, and N-allylmaleimide was synthesized and purified in the same manner.

【００２２】実施例５ 無水マレイン酸９８ｇをＮ，Ｎ−ジメチルホルムアミド
５００ｇ中に溶解し、これとは別にアリルアミン５７ｇ
をＮ，Ｎ−ジメチルホルムアミド３００ｇ中に溶解し
た。アリルアミン溶液を無水マレイン酸溶液中へ少量ず
つ滴下し、８時間室温で反応させた。次いで無水酢酸１
２２ｇ、トリエチルアミン２０ｇ及び酢酸カリウム９．
８ｇを加え、更に８時間３０℃で反応させた。この溶液
を１０ｋｇの水中へ投入し、析出した固体を濾過して集
め、Ｎ−アリルマレイミドの粗製物を得た。以下、実施
例１と同様に精製を行った。Example 5 98 g of maleic anhydride was dissolved in 500 g of N, N-dimethylformamide, and separately, 57 g of allylamine.
Was dissolved in 300 g of N, N-dimethylformamide. The allylamine solution was dropped little by little into the maleic anhydride solution, and the mixture was reacted at room temperature for 8 hours. Then acetic anhydride 1
22 g, triethylamine 20 g and potassium acetate 9.
8 g was added, and the mixture was further reacted at 30 ° C. for 8 hours. This solution was poured into 10 kg of water, and the precipitated solid was collected by filtration to obtain a crude product of N-allylmaleimide. Then, purification was performed in the same manner as in Example 1.

【００２３】比較例１ 実施例１において合成したＮ−アリルマレイミド粗製物
をクロロホルム８００ｇに溶解し、次いでイオン交換水
３５０ｇを加え激しく撹拌した。１時間後、水層の約半
量が分離したが、残りの水層とクロロホルム層は混濁状
態のまま分離しなかった。更に１８時間静置後、水層の
９割以上が分離した後有機層を分離し、エバポレーショ
ン、乾燥を行った。ゲルパーミエーションクロマトグラ
フィー及び抽出液電導度の分析により精製の効果を確認
した（表１）Comparative Example 1 The crude N-allylmaleimide synthesized in Example 1 was dissolved in 800 g of chloroform, 350 g of ion-exchanged water was added, and the mixture was vigorously stirred. After 1 hour, about half of the aqueous layer was separated, but the remaining aqueous layer and chloroform layer remained turbid and did not separate. After still standing for 18 hours, 90% or more of the aqueous layer was separated, and then the organic layer was separated, evaporated and dried. The effect of purification was confirmed by gel permeation chromatography and analysis of the conductivity of the extract (Table 1).

【００２４】比較例２ 実施例１において合成したＮ−アリルマレイミド粗製物
をクロロホルム８００ｇに溶解し、次いで１％食塩水３
５０ｇを加え激しく撹拌した。数分後、水層とクロロホ
ルム層は完全に分離した。以下、実施例１と同様に精製
を行い、精製の効果を確認した。Comparative Example 2 The crude N-allylmaleimide synthesized in Example 1 was dissolved in 800 g of chloroform, and then 3% of 1% saline solution was added.
50 g was added and vigorously stirred. After a few minutes, the aqueous layer and the chloroform layer were completely separated. Thereafter, purification was performed in the same manner as in Example 1, and the effect of purification was confirmed.

【００２５】比較例３ 実施例１において合成したＮ−アリルマレイミド粗製物
をクロロホルム８００ｇに溶解し、ｎ−ヘキサン２００
ｇを加え、次いでイオン交換水３５０ｇを加え激しく撹
拌した。３時間後、水層の約半量が分離したが、残りの
水層と有機層は混濁状態のまま分離しなかった。また、
水層と混濁層の界面に多量の黒色の海綿状物質が浮遊し
た。７２時間後、水層の９割以上が分離したが、界面の
浮遊物質は変化しなかったため有機層を単離することは
できなかった。Comparative Example 3 The crude N-allylmaleimide synthesized in Example 1 was dissolved in 800 g of chloroform, and n-hexane 200 was added.
g, then 350 g of ion-exchanged water was added, and the mixture was vigorously stirred. After 3 hours, about half of the aqueous layer was separated, but the remaining aqueous layer and organic layer remained turbid and did not separate. Also,
A large amount of black spongy material floated at the interface between the water layer and the turbid layer. After 72 hours, 90% or more of the aqueous layer was separated, but the floating material at the interface did not change, and the organic layer could not be isolated.

【００２６】比較例４ 実施例１において合成したＮ−アリルマレイミド粗製物
をトルエン−メタノール混合溶剤を用いて再結晶を行っ
た。析出した結晶を集めて秤量した結果、実施例１にお
いて得られた精製品の６３％の収量しか得られなかっ
た。ゲルパーミエーションクロマトグラフィー及び抽出
液電導度の分析により精製の効果を確認した（表１）Comparative Example 4 The N-allylmaleimide crude product synthesized in Example 1 was recrystallized using a toluene-methanol mixed solvent. As a result of collecting and weighing the precipitated crystals, only 63% of the purified product obtained in Example 1 was obtained. The effect of purification was confirmed by gel permeation chromatography and analysis of the conductivity of the extract (Table 1).

【００２７】[0027]

【表１】 [Table 1]

【００２８】[0028]

【発明の効果】本発明により自己重合性モノマーの粗製
物を温和で生産性の高い方法により高純度に精製するこ
とが可能となった。According to the present invention, a crude product of a self-polymerizable monomer can be purified to a high purity by a mild and highly productive method.

Claims (5)

【特許請求の範囲】[Claims] 【請求項１】 自己重合性モノマー粗製物を非水系溶剤
〔１〕に溶解し、次いで得られた溶液に、非水系溶剤
〔１〕と相溶し、かつ非水系溶剤〔１〕中に溶解してい
る有機性不純物を選択的に沈澱させる別種の非水系溶剤
〔２〕並びにアルカリ金属塩、アルカリ土類金属塩及び
アンモニウム塩から選ばれる塩〔３〕を添加し、次いで
水を混合して不純物を水中に抽出除去した後、生成した
沈殿と有機層と水層とを分離し、有機層から自己重合性
モノマーを回収することを特徴とする自己重合性モノマ
ーの精製法。1. A crude self-polymerizable monomer is dissolved in a non-aqueous solvent [1], and then the resulting solution is compatible with the non-aqueous solvent [1] and dissolved in the non-aqueous solvent [1]. A non-aqueous solvent [2] for selectively precipitating organic impurities present therein and a salt [3] selected from alkali metal salts, alkaline earth metal salts and ammonium salts, and then mixed with water. A method for purifying a self-polymerizable monomer, which comprises extracting and removing impurities from water, separating the generated precipitate from the organic layer and the aqueous layer, and recovering the self-polymerizable monomer from the organic layer. 【請求項２】 自己重合性モノマーが式Ｉに示すマレイ
ミド化合物である請求項１記載の自己重合性モノマーの
精製法。 【化１】 （ＲはＣ、Ｈ、Ｎ、Ｏ、Ｓのうちのいずれかの元素の組
み合わせによって構成される脂肪族又は芳香族の基を示
し、ｎは１以上の整数を示す。）2. The method for purifying a self-polymerizable monomer according to claim 1, wherein the self-polymerizable monomer is a maleimide compound represented by formula I. [Chemical 1] (R represents an aliphatic or aromatic group composed of a combination of any one of C, H, N, O, and S, and n represents an integer of 1 or more.) 【請求項３】 非水系溶剤〔１〕が有機ハロゲン化炭化
水素系溶剤であり、非水系溶剤〔２〕が脂肪族飽和炭化
水素系溶剤である請求項１又は２記載の自己重合性モノ
マーの精製法。3. The self-polymerizable monomer according to claim 1, wherein the non-aqueous solvent [1] is an organic halogenated hydrocarbon solvent and the non-aqueous solvent [2] is an aliphatic saturated hydrocarbon solvent. Purification method. 【請求項４】 塩〔３〕が炭酸塩、炭酸水素塩、酢酸塩
及びシュウ酸塩から選ばれるいずれかである請求項１、
２又は３記載の自己重合性モノマーの精製法。4. The salt [3] is any one selected from carbonate, hydrogencarbonate, acetate and oxalate.
The method for purifying the self-polymerizable monomer according to 2 or 3. 【請求項５】 非水系溶剤〔１〕に対する非水系溶剤
〔２〕及び塩〔３〕の添加量が、それぞれ、重量比で
〔１〕／〔２〕＝９５／５〜７０／３０及び〔１〕／
〔３〕＝９９．９９／０．０１〜９９．９０／０．１０
である請求項１、２、３又は４記載の自己重合性モノマ
ーの精製法。5. A non-aqueous solvent [2] and a salt [3] are added in a weight ratio of [1] / [2] = 95/5 to 70/30 and [5] to the non-aqueous solvent [1], respectively. 1] /
[3] = 99.99 / 0.01 to 99.90 / 0.10
The method for purifying a self-polymerizing monomer according to claim 1, 2, 3, or 4.