JPS6341455A - Purification of bismaleimides - Google Patents
Purification of bismaleimidesInfo
- Publication number
- JPS6341455A JPS6341455A JP18417586A JP18417586A JPS6341455A JP S6341455 A JPS6341455 A JP S6341455A JP 18417586 A JP18417586 A JP 18417586A JP 18417586 A JP18417586 A JP 18417586A JP S6341455 A JPS6341455 A JP S6341455A
- Authority
- JP
- Japan
- Prior art keywords
- bismaleimides
- carbon dioxide
- temperature
- bismaleimide
- 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.)
- Pending
Links
- 229920003192 poly(bis maleimide) Polymers 0.000 title claims abstract description 60
- 238000000746 purification Methods 0.000 title claims description 8
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 60
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 30
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims description 25
- 239000000126 substance Substances 0.000 claims description 10
- 239000012043 crude product Substances 0.000 claims description 7
- 238000000605 extraction Methods 0.000 abstract description 9
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 abstract description 7
- 238000010438 heat treatment Methods 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 3
- 150000001875 compounds Chemical class 0.000 abstract description 2
- 229920005989 resin Polymers 0.000 abstract description 2
- 239000011347 resin Substances 0.000 abstract description 2
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 abstract 1
- 239000007795 chemical reaction product Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 7
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 6
- 238000000354 decomposition reaction Methods 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 150000007513 acids Chemical class 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000003377 acid catalyst Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000012024 dehydrating agents Substances 0.000 description 2
- 239000000539 dimer Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- GVYHDVHOWAIYEH-UHFFFAOYSA-N 4-azatricyclo[5.2.2.02,6]undeca-1,6,8,10-tetraene-3,5-dione Chemical compound C1=CC2=CC=C1C1=C2C(=O)NC1=O GVYHDVHOWAIYEH-UHFFFAOYSA-N 0.000 description 1
- JFMOYHBEGWPXBI-UHFFFAOYSA-N [C].[As] Chemical compound [C].[As] JFMOYHBEGWPXBI-UHFFFAOYSA-N 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- -1 amine compound Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 238000001640 fractional crystallisation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 210000004894 snout Anatomy 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Pyrrole Compounds (AREA)
Abstract
Description
【発明の詳細な説明】 （産業上の利用分野） 本発明は新規なビスマレイミド類の精製方法に関する。[Detailed description of the invention] (Industrial application field) The present invention relates to a novel method for purifying bismaleimides.
詳しくは、超臨界状態の二酸化炭素を用いてごスマレイ
ミド類の粗ＩｙＪ物からビスマレイミド類を抽出分離す
るビスマレイミド類の精製方法に関する。Specifically, the present invention relates to a method for purifying bismaleimides by extracting and separating bismaleimides from a crude IyJ product of smaleimides using carbon dioxide in a supercritical state.
ビスマレイミド類は樹脂原料、医薬品、農薬等の原料と
して広く使用されている。Bismaleimides are widely used as raw materials for resins, pharmaceuticals, agricultural chemicals, etc.
（従来技術）
ビスマレイミド類を製造する方法としては各種のものが
知られている。−役向なものとしては、０） 無水マ
レイン酸とアミン化合物とを有機溶媒中で反応さｕ１生
成するマレインアミド酸類を単離し、単離したマレイン
アミド酸類を無水酢酸のような脱水剤を用いてイミド化
させる方法が米国特許用２．４４４．５３６号明細書に
開示されている。(Prior Art) Various methods are known for producing bismaleimides. - As for the useful things, 0) Isolate the maleamic acids produced by reacting maleic anhydride and an amine compound in an organic solvent, and use a dehydrating agent such as acetic anhydride to isolate the maleamic acids that are produced. A method of imidization is disclosed in US Pat. No. 2,444,536.
■ 生成したマレインアミド酸類を６機溶媒から単離す
ることなしにこの反応混合物に酸触媒を添加してイミド
化する方法が特公昭５１−６８００号Ｊ５よび特開昭５
７−１５９７６４号公報明細書等に数多く開示されてい
る。■ A method of imidizing the generated maleamic acids by adding an acid catalyst to the reaction mixture without isolating them from the solvent is disclosed in Japanese Patent Publication No. 51-6800 J5 and Japanese Patent Publication No. 51-6800.
Many of these are disclosed in the specification of Japanese Patent Publication No. 7-159764.
しかしながらこれらの何れのビスマレイミド類の製造方
法においても問題があり、イミド化反応の過程において
無視しえない借の副生成物が生成し、高純度のビスマレ
イミド類を得ようとづれば精製する必要がある。However, there are problems with any of these methods for producing bismaleimides, as non-negligible by-products are produced during the imidization reaction, and purification is necessary in order to obtain high-purity bismaleimides. There is.
従来、ヒスマレイミド類の精製方法としては、（１）
反応液を大量の冷水中へ注入して、析出する結晶をｒ
戸別し、この結晶を更に多量の水で洗浄したり、或いは
稀薄な炭酸ナトリウム水溶液や苛性ソーダ水溶液で洗浄
したのち乾燥させる方法が特開昭５７−１５９７６４号
公報明細書に開示されている。Conventionally, methods for purifying hismaleimides include (1)
Pour the reaction solution into a large amount of cold water to remove the precipitated crystals.
JP-A-57-159764 discloses a method in which the crystals are separated from each other, washed with a large amount of water, or washed with a dilute aqueous sodium carbonate solution or aqueous caustic soda solution, and then dried.
■ ビスマレイミド類の組成物をアセトニトリル、ジオ
キサン、テトラヒドロフラン等の有機溶媒を用いて再結
晶し分離積装する方法が特開昭５６−８７５６０号公報
明細書に開示されている。(2) A method in which a composition of bismaleimides is recrystallized using an organic solvent such as acetonitrile, dioxane, or tetrahydrofuran and then separated and loaded is disclosed in the specification of JP-A-56-87560.
しかし、上記のような方法では、イミド化工程で生成す
る副生成物が樹脂状の物質ヤ）ビスマレイミド類と同様
に炭酸ナトリウム水溶液に不溶性の物質であること、あ
るいは再結晶工程が複雑となり、経済的でなく、また有
！ｆｉ溶媒の除去が完全に行なえない等、品質、経済性
の面で満足できる高純度のビスマレイミド類を得ること
は困難である。However, in the above method, the by-products generated in the imidization step are resin-like substances, substances that are insoluble in sodium carbonate aqueous solution like bismaleimides, or the recrystallization step is complicated. Not economical, but also possible! It is difficult to obtain bismaleimides of high purity that are satisfactory in terms of quality and economy, as the fi solvent cannot be completely removed.
（発明が解決しようとする問題点）
ビスマレイミド類には蒸留による精製方法もあるが、ビ
スマレイミド類は沸点が高く、しかもその分子内に反応
性に富むエチレン型不飽和結合を有しているために蒸留
塔内で加熱されることにより重合、分解、着色が促進さ
れる。(Problem to be solved by the invention) Bismaleimides can be purified by distillation, but bismaleimides have a high boiling point and have highly reactive ethylenically unsaturated bonds in their molecules. Therefore, polymerization, decomposition, and coloration are promoted by heating in the distillation column.
その結果、蒸留精製収率が低く、しかも分解によって生
成する不純物が製品に混入し、製品の品質を低下させて
いる。As a result, the distillation purification yield is low, and impurities generated by decomposition are mixed into the product, degrading the quality of the product.
一方、再結晶法または分別結晶法ではビスマレイミド類
の粗製物に含まれているダイマー等の分離が十分に行な
えず、しかも溶媒の除去に多大のエネルギーを要し、し
かも溶媒の完全な除去が不可能であるなど、従来の技術
では精製収率、品質、経済性の点で満足のできる製品を
得ることが困難であった。On the other hand, the recrystallization method or the fractional crystallization method cannot sufficiently separate the dimer etc. contained in the crude product of bismaleimides, requires a large amount of energy to remove the solvent, and is difficult to completely remove the solvent. With conventional techniques, it has been difficult to obtain products that are satisfactory in terms of purification yield, quality, and economic efficiency.
本発明者等は上記問題点を解決づるため鋭怠検詞した結
果、ビスマレイミド類がそのダイマー、重合高分子、着
色物質など、ビスマレイミド類の粗製物に含まれる不純
物に比較し、格段に超臨界二酸化炭素への溶解度が大ぎ
く、そのためヒスマレイミド類の粗製物に超臨界状態の
二酸化炭素を接触させることにより、ビスマレイミド類
の粗製物から主としてビスマレイミド類を超臨界二酸化
炭素に抽出溶解させ、ビスマレイミド類の溶解度が温度
または／および圧力を低下させることによって著しく低
下することを利用して高純度のビスマレイミド類を分離
回収できることを見い出し、本発明を完成した。The inventors of the present invention have conducted extensive research to solve the above-mentioned problems, and have found that bismaleimides contain significantly more impurities than the impurities contained in crude products of bismaleimides, such as their dimers, polymeric polymers, and colored substances. The solubility in supercritical carbon dioxide is high, so by bringing the crude hismaleimides into contact with carbon dioxide in a supercritical state, mainly bismaleimides can be extracted and dissolved in supercritical carbon dioxide from the crude bismaleimides. The present invention was completed based on the discovery that high-purity bismaleimides can be separated and recovered by utilizing the fact that the solubility of bismaleimides is significantly reduced by lowering temperature and/or pressure.
（問題を解決するための手段）
本発明は
一般式（１）、
ＯＯ
ＩＩ １１
ＣＨ−ＣＣ−ＣＨ
ＩＩ Ｎ−Ｚ−Ｎ ＩＩ
（１）ＣＨ−ＣＣ−ＣＨ
で示されるビスマレイミド類の粗製物に超臨界状態の二
酸化炭素を接触させて得られる、ビスマレイミド類を含
有する二酸化炭素からビスマレイミド類を分離回収する
ことを特徴とするビスマレイミド類のＴｉｅｈ法に関す
るｂのである。(Means for Solving the Problem) The present invention has the general formula (1), OO II 11 CH-CC-CH II N-Z-N II
(1) A feature of separating and recovering bismaleimides from carbon dioxide containing bismaleimides, which is obtained by contacting a crude product of bismaleimides represented by CH-CC-CH with carbon dioxide in a supercritical state. b concerning the Tieh method for bismaleimides.
本発明の超臨界状態の二酸化炭素は、温度３１゜１℃〜
２００℃、圧力が７４．２〜５００に９／ｃｒＡＧ１好
ましくは温度４０〜１４０℃、圧カフ５〜３００ Ｋ９
／ ｃｉ Ｇの範囲が抽出条件として採用できる。The supercritical carbon dioxide of the present invention has a temperature of 31°1°C to
200℃, pressure 74.2-500 9/crAG1 preferably temperature 40-140℃, pressure cuff 5-300K9
/ ci G range can be adopted as the extraction condition.
本発明の抽出条件は、温度および圧力が共に高い方がビ
スマレイミド類の溶解度が大きく、抽出効率を向上させ
ることができる。Regarding the extraction conditions of the present invention, the higher the temperature and pressure are, the higher the solubility of bismaleimides is, and the extraction efficiency can be improved.
しかし抽出圧力を高めることは一方で高圧設備の費用の
増大を招き、経済性の問題を生じる。また抽出温度を上
げることは抽出目的物であるビスマレイミド類の重合、
分解、着色等の変質を促進させるものである。However, increasing the extraction pressure on the other hand increases the cost of high-pressure equipment, creating an economical problem. In addition, increasing the extraction temperature may lead to the polymerization of bismaleimides, which are the extraction targets.
It promotes deterioration such as decomposition and coloring.
一方、ビスマレイミド類を含む二酸化炭素から、ヒスマ
レイミド類を分離するには温度を下げ、または／および
圧力を下げ、その結果溶解度を下げることによってビス
マレイミド類のみを析出ざける方法がある。On the other hand, in order to separate hismaleimides from carbon dioxide containing bismaleimides, there is a method in which only the bismaleimides are precipitated by lowering the temperature and/or pressure, thereby lowering the solubility.
本発明が対像とするビスマレイミド類の粗Ｓ！吻は従来
公知の製造方法によって得られるものである。すなわち
、原料マレインアミド酸類は通常無水マレイン酸とアミ
ン類との反応により容易に得られるものであり、このも
ののイミド化閉環反応としては、本川［１ｍの従来技術
の項で既に記述したように、マレインアミド酸類を有機
溶媒から単離することなしに酸触媒の存在下に直接加熱
してイミド化させる方法、あるいは無水酢酸のような脱
水剤を用いてイミド化させる方法などがあり、いずれの
方法によって製造されるビスマレイミド類の粗製物も本
発明の精製方法は優れた効果を与える。Crude S! of bismaleimides targeted by the present invention! The snout is obtained by a conventionally known manufacturing method. That is, the raw material maleamic acids are usually easily obtained by the reaction of maleic anhydride and amines, and the imidization ring-closing reaction of this material is carried out by the method described in the prior art section of Motokawa [1m]. There are two methods: imidization by direct heating in the presence of an acid catalyst without isolating maleamic acids from an organic solvent, or imidization using a dehydrating agent such as acetic anhydride. The purification method of the present invention also provides excellent effects on the crude bismaleimides produced by the method.
上述の方法によって得られるヒスマレイミド類は例えば
、
一般式（１）、
ＩＩ １１
ＣＨ−ＣＣ−ＣＨ
ＩＩ Ｎ−Ｚ−Ｎ ＩＩ
（１）ＣＨ−ＣＣ−Ｃ１１
＋１ １
ｏ Ｏ
で表わされるものであり、さらに具体的に例示するなら
ば、Ｎ、 Ｎ−−ｐ−フェニレンビスマレイミド、Ｎ、
Ｎ−−ｍ−７エニレンビスマレイミド、Ｎ、Ｎ−−（メ
チレン−ジーρ−フェニレンビスマレイミド、Ｎ、Ｎ”
−（オキシ−ジ−ｐ−フェニレンビスマレイミドが挙げ
られる。Hismaleimides obtained by the above method have, for example, the general formula (1), II 11 CH-CC-CH II N-Z-N II
(1) It is represented by CH-CC-C11 +1 1 o O, and more specific examples include N, N--p-phenylene bismaleimide, N,
N--m-7 enylene bismaleimide, N, N--(methylene-di-ρ-phenylene bismaleimide, N, N"
-(oxy-di-p-phenylene bismaleimide).
（作 用）
本発明によれば、超臨界二酸化炭素はビスマレイミド類
に対しで高い溶解能を有する。そのため、高い沸点を有
するヒスマレイミド類を、ビスマレイミド類の粗製物か
ら比較的低い温度で溶解し抽出することができる。そう
することによって、ビスマレイミド類はその分子内に反
応性に富む二重結合をイアするにもかかわらず、抽出操
作中に重合、分解、着色物質生成等によるビスマレイミ
ド類のむ失および品質劣化が起ることを防ぐことができ
る。(Function) According to the present invention, supercritical carbon dioxide has a high ability to dissolve bismaleimides. Therefore, hismaleimides having a high boiling point can be dissolved and extracted from the crude bismaleimides at a relatively low temperature. By doing so, even though bismaleimides have highly reactive double bonds in their molecules, bismaleimides are lost and quality deteriorates due to polymerization, decomposition, formation of colored substances, etc. during the extraction procedure. can be prevented from occurring.
また、超臨界二酸化炭素はビスマレイミド類に対してビ
スマレイミド類の粗製物中に含有される手合物、分解物
、着色物質等の不純物に比較して、格段に大きな溶解能
を右する。Furthermore, supercritical carbon dioxide has a much greater dissolving power for bismaleimides than impurities such as compounds, decomposition products, and colored substances contained in crude bismaleimides.
したがって、ｉｆ！１臨界二酸化炭素を使用することに
よって、ビスマレイミド類の粗製物からはとんどビスマ
レイミドのみを選択的に抽出することができる。さらに
髪よ、ビスマレイミド類のηｌ’ｌをｉｉ！１臨界二酸
化炭素抽出処理して（すられるビスマレイミド類を含有
する二酸化炭素からビスマレイミド類を分離するには、
単に温度または／および圧力を下げるだけで良く、重合
、分解等のにる危険性のある加熱操作を必要としない。Therefore, if! By using 1-critical carbon dioxide, only bismaleimide can be selectively extracted from the crude product of bismaleimides. Furthermore, hair, ηl'l of bismaleimides! 1. To separate bismaleimides from carbon dioxide containing bismaleimides by critical carbon dioxide extraction treatment,
It is sufficient to simply lower the temperature and/or pressure, and there is no need for heating operations that may lead to polymerization, decomposition, or the like.
したがって、本発明によればビスマレイミド類の粗製物
に超臨界二酸化炭素を作用させることによって、ビスマ
レイミド類の純度・品質の良好なしのをしかも収率よく
得ることができる作用をイｊする。Therefore, according to the present invention, bismaleimides of good purity and quality can be obtained in good yield by applying supercritical carbon dioxide to a crude product of bismaleimides.
（実 施 例）
以下、本発明の実施例を示すが、本発明はこれらに限定
されるものでない。(Examples) Examples of the present invention will be shown below, but the present invention is not limited thereto.
実施例 １
純度９４．４重量％のＮ、Ｎ＝−ｐ−フェニレンビスマ
レイミドの粗製物４０．０ｇを０．３ｊ！のステンレス
製耐圧容器に仕込み、ガス吹き込み口より二酸化炭素を
供給し、容器内をａ度５０℃、圧力２００ Ｋ９ ／
ｃｉ Ｇに保ちながら、一方のガス抜き出し口から連続
的にＮ、Ｎ”−ｏ−フェニレンビスマレイミドを含有す
る超臨界二酸化炭素を扱き出し、ゼバレーターで常温、
大気圧とし二酸化炭素と抽出物３６．４ｑとに分離した
。１ｑられた抽出物は白色結晶であり、１Ｆ、Ｉられた
Ｎ、Ｎ−−Ｄ−フェニレンビスマレイミドの純度は９９
．４重量％であった。Example 1 0.3j! of 40.0g of crude N,N=-p-phenylene bismaleimide with a purity of 94.4% by weight! Carbon dioxide is supplied from the gas inlet, and the inside of the container is heated to a temperature of 50°C and a pressure of 200 K9/.
Supercritical carbon dioxide containing N,N''-o-phenylene bismaleimide was continuously drawn out from one gas outlet while maintaining the temperature at ciG, and heated at room temperature in a zebalator.
It was brought to atmospheric pressure and separated into carbon dioxide and 36.4q of extract. The extracted extract is a white crystal, and the purity of the extracted N,N--D-phenylene bismaleimide is 99.
．． It was 4% by weight.
実施例 ２
純度９３．８車量％のＮ、Ｎ′−（メチレン−ジ−ｐ−
フェニレンごスマレイミドの粗製物４０゜０ｇを０．３
１のステンレス製耐圧ＰＪ器に仕込み、ガス吹き込み口
より二酸化炭素を供給し、容器内を温度５０℃、圧力２
００ Ｋ９ ／ ｃｉ Ｇに保らながら、一方のガス扱
き出し口から連続的にＮ、Ｎ−−（メヂレンージーｐ−
〕１ニレンビスマレイミドを含イ”ｉづる超臨界二酸（
ヒ炭素を汰き出し、ヒバレータ−で常温、大気圧とし二
酸化炭素と抽出物３６．４ｇとに分離した。得られた抽
出物は白色結晶であり、１りられたＮ、Ｎ”−（メチレ
ン−ジ−ｐ−フェニレンビスマレイミドの純度は９９．
１重間％であった。Example 2 N, N'-(methylene-di-p-
40゜0g of crude phenylene maleimide 0.3
1 into a stainless steel pressure-resistant PJ container, supply carbon dioxide from the gas inlet, and maintain the inside of the container at a temperature of 50°C and a pressure of 2.
00 K9 / ci While maintaining G, N, N-- (medium range p-
] 1 supercritical diacid containing nylene bismaleimide (
The arsenic carbon was pumped out and brought to room temperature and atmospheric pressure using a hibernator and separated into carbon dioxide and 36.4 g of extract. The obtained extract was white crystals, and the purity of the extracted N,N''-(methylene-di-p-phenylene bismaleimide) was 99.
It was 1% by weight.
（発明の効果）
本発明によれば、ヒスマレイミド類粗製物に超臨界二酸
化炭素を作用させることによって、ビスマレイミド類の
純度・品質の良好なものをしかも収率よく得ることがで
きる。(Effects of the Invention) According to the present invention, bismaleimides with good purity and quality can be obtained in good yield by allowing supercritical carbon dioxide to act on a crude product of hismaleimides.
従来、沸点が高く蒸留できなかったものや再結晶法等で
の残存溶媒の除去を必要とする製品は純度および収率が
低く、あるいは工程が複雑となることによって経済性に
難点があったが、これによって本発明では十分に工業的
規模でｌｋ度９８重量％以上のヒスマレイミド類が１１
１られる。In the past, products with high boiling points that could not be distilled or products that required removal of residual solvent by recrystallization methods had low purity and yield, or were economically difficult due to complicated processes. As a result, in the present invention, on an industrial scale, hismaleimides having a lk degree of 98% by weight or more can be produced at 11% by weight.
1 will be given.
Claims (3)
数式、化学式、表等があります▼、 ▲数式、化学式、表等があります▼および ▲数式、化学式、表等があります▼を示す。〕 で示されるビスマレイミド類の粗製物に超臨界状態の二
酸化炭素を接触させて得られる、ビスマレイミド類を含
有する二酸化炭素からビスマレイミド類を分離回収する
ことを特徴とするビスマレイミド類の精製方法。(1) General formula (1), ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (1) [In the formula, Z is ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲
There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ and ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼. ] Purification of bismaleimides characterized by separating and recovering bismaleimides from carbon dioxide containing bismaleimides, which is obtained by contacting the crude product of bismaleimides represented by supercritical carbon dioxide with carbon dioxide containing bismaleimides. Method.
０℃、圧力が７４．２〜５００Ｋｇ／ｃｍ＾２の範囲で
あることを特徴とする特許請求の範囲第１項の精製方法
。(2) Supercritical carbon dioxide has a temperature of 31.1°C to 20°C
The purification method according to claim 1, characterized in that the temperature is 0° C. and the pressure is in the range of 74.2 to 500 kg/cm^2.
圧力７５〜３００Ｋｇ／ｃｍ＾２の範囲であることを特
徴とする特許請求の範囲第１項の精製方法。(3) Carbon dioxide in a supercritical state has a temperature of 40 to 140°C,
The purification method according to claim 1, characterized in that the pressure is in the range of 75 to 300 kg/cm^2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18417586A JPS6341455A (en) | 1986-08-07 | 1986-08-07 | Purification of bismaleimides |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18417586A JPS6341455A (en) | 1986-08-07 | 1986-08-07 | Purification of bismaleimides |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS6341455A true JPS6341455A (en) | 1988-02-22 |
Family
ID=16148674
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP18417586A Pending JPS6341455A (en) | 1986-08-07 | 1986-08-07 | Purification of bismaleimides |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6341455A (en) |
-
1986
- 1986-08-07 JP JP18417586A patent/JPS6341455A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JPH0140028B2 (en) | ||
| JPS61229862A (en) | Method of purifying maleimide | |
| Hoffmann et al. | Some observations on the synthesis of phthaloylamino acids | |
| JPS6341455A (en) | Purification of bismaleimides | |
| US4510100A (en) | Process for the production of 2-amino-1-naphthalenesulfonic acid | |
| JPH11130706A (en) | Production of 4,4'-bischloromethylbiphenyl | |
| JPS6339858A (en) | Purification of phenylmaleimide | |
| RU2323207C1 (en) | Method for preparing chloro-substituted aromatic carboxylic acid aminoanilides | |
| JPS62123168A (en) | Production of maleimide compound | |
| JPS58157727A (en) | Production of aromatic compound with chlorinated nuleus | |
| JPS5829305B2 (en) | Marei Midono Seizouhou | |
| US5523472A (en) | Process for the preparation of 5-fluoroanthranilic acid | |
| JP4626031B2 (en) | Method for producing high purity pyromellitic acid and high purity pyromellitic anhydride | |
| US4973752A (en) | Novel process to prevent formation of chlorinated by-products in APAP production | |
| JPS62238262A (en) | Purification of maleimide | |
| JPH07206763A (en) | Production of purified 3,3',4,4',-biphenyltetracarboxylic acid or its acid dianhydride | |
| Kurita et al. | Diphthalimido carbonate: A new reagent for active ester synthesis | |
| JPS63425B2 (en) | ||
| US3663546A (en) | Process for the preparation of pyridazone derivatives | |
| JPS61204166A (en) | Purification of maleimide | |
| JPS6125713B2 (en) | ||
| SU1728228A1 (en) | Method of 9,9-bis-(4-aminophenyl)-fluorene synthesis | |
| JPH0770124A (en) | Production of acetylguanine | |
| JPH07116096B2 (en) | Method for producing high-purity 0-toluic acid | |
| US1930753A (en) | Chlorination of cresidine |