JPS62273952A - Production of n-phenylmaleimide - Google Patents
Production of n-phenylmaleimideInfo
- Publication number
- JPS62273952A JPS62273952A JP11477786A JP11477786A JPS62273952A JP S62273952 A JPS62273952 A JP S62273952A JP 11477786 A JP11477786 A JP 11477786A JP 11477786 A JP11477786 A JP 11477786A JP S62273952 A JPS62273952 A JP S62273952A
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- phenylmaleimide
- charged
- maleic anhydride
- aniline
- 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.)
- Granted
Links
- HIDBROSJWZYGSZ-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC=C1 HIDBROSJWZYGSZ-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 15
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 44
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000003054 catalyst Substances 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 230000002378 acidificating effect Effects 0.000 claims abstract description 15
- 239000002994 raw material Substances 0.000 claims abstract description 14
- 238000006482 condensation reaction Methods 0.000 claims description 15
- 239000012535 impurity Substances 0.000 abstract description 11
- 238000005406 washing Methods 0.000 abstract description 8
- 150000001875 compounds Chemical class 0.000 abstract description 4
- 239000011347 resin Substances 0.000 abstract description 2
- 229920005989 resin Polymers 0.000 abstract description 2
- 229920001187 thermosetting polymer Polymers 0.000 abstract description 2
- 230000005494 condensation Effects 0.000 abstract 1
- 238000009833 condensation Methods 0.000 abstract 1
- 238000004821 distillation Methods 0.000 description 13
- 239000000243 solution Substances 0.000 description 12
- 239000002904 solvent Substances 0.000 description 9
- 239000007795 chemical reaction product Substances 0.000 description 8
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical compound O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 8
- IYMZEPRSPLASMS-UHFFFAOYSA-N 3-phenylpyrrole-2,5-dione Chemical compound O=C1NC(=O)C(C=2C=CC=CC=2)=C1 IYMZEPRSPLASMS-UHFFFAOYSA-N 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 6
- 239000012141 concentrate Substances 0.000 description 5
- 238000006386 neutralization reaction Methods 0.000 description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000008346 aqueous phase Substances 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 229960002317 succinimide Drugs 0.000 description 4
- 239000008096 xylene Substances 0.000 description 4
- JZODKRWQWUWGCD-UHFFFAOYSA-N 2,5-di-tert-butylbenzene-1,4-diol Chemical compound CC(C)(C)C1=CC(O)=C(C(C)(C)C)C=C1O JZODKRWQWUWGCD-UHFFFAOYSA-N 0.000 description 3
- XPRGFWCOARUGAL-UHFFFAOYSA-N 3-anilino-1-phenylpyrrolidine-2,5-dione Chemical compound O=C1N(C=2C=CC=CC=2)C(=O)CC1NC1=CC=CC=C1 XPRGFWCOARUGAL-UHFFFAOYSA-N 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 3
- 239000011976 maleic acid Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003377 acid catalyst Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 238000004811 liquid chromatography Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000001577 simple distillation Methods 0.000 description 2
- WHZLCOICKHIPRL-VOTSOKGWSA-N (e)-4-anilino-4-oxobut-2-enoic acid Chemical compound OC(=O)\C=C\C(=O)NC1=CC=CC=C1 WHZLCOICKHIPRL-VOTSOKGWSA-N 0.000 description 1
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 1
- XRCRJFOGPCJKPF-UHFFFAOYSA-N 2-butylbenzene-1,4-diol Chemical compound CCCCC1=CC(O)=CC=C1O XRCRJFOGPCJKPF-UHFFFAOYSA-N 0.000 description 1
- BUXMOFUBRLIEHQ-UHFFFAOYSA-N 3-anilinopyrrolidine-2,5-dione Chemical compound O=C1NC(=O)CC1NC1=CC=CC=C1 BUXMOFUBRLIEHQ-UHFFFAOYSA-N 0.000 description 1
- XESZUVZBAMCAEJ-UHFFFAOYSA-N 4-tert-butylcatechol Chemical compound CC(C)(C)C1=CC=C(O)C(O)=C1 XESZUVZBAMCAEJ-UHFFFAOYSA-N 0.000 description 1
- 101100433727 Caenorhabditis elegans got-1.2 gene Proteins 0.000 description 1
- 239000007832 Na2SO4 Substances 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000000199 molecular distillation Methods 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- -1 p-substituted anilines Chemical class 0.000 description 1
- LRTFPLFDLJYEKT-UHFFFAOYSA-N para-isopropylaniline Chemical compound CC(C)C1=CC=C(N)C=C1 LRTFPLFDLJYEKT-UHFFFAOYSA-N 0.000 description 1
- LQJARUQXWJSDFL-UHFFFAOYSA-N phenamine Chemical compound CCOC1=CC=C(NC(=O)CN)C=C1 LQJARUQXWJSDFL-UHFFFAOYSA-N 0.000 description 1
- 229950010879 phenamine Drugs 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000003586 protic polar solvent Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 150000004992 toluidines Chemical class 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
Landscapes
- Pyrrole Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
３、発明の詳細な説明
（産業上の利用分野）
本発明は、不純物の副生が有効に防止され且つ収率が顕
著に向上したＮ−フェニルマレイミドの製造方法に関す
る。Detailed Description of the Invention 3. Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a method for producing N-phenylmaleimide in which the by-production of impurities is effectively prevented and the yield is significantly improved. .
（従来技術及びその問題点）
無水マレイン酸とアニリンとを反応させてフェニルマレ
イミドを製造する方法は従来公知である。(Prior Art and its Problems) A method for producing phenylmaleimide by reacting maleic anhydride with aniline is conventionally known.
従来公知のこの製造方法は、無水マレイン酸とアニリン
とを等モル用いて縮合反応を行なうものであるが、Ｎ−
フェニルマレイミドにアニリンが付加した化合物すなわ
ち、Ｎ−７エニルー（２−アニリノ）スクシンイミド等
の除去困難な不純物が多量に副生じ、目的とするフェニ
ルマレイミドの収率が低いという問題点を有している。In this conventionally known production method, a condensation reaction is carried out using equimolar amounts of maleic anhydride and aniline.
The problem is that a large amount of difficult-to-remove impurities such as a compound in which aniline is added to phenylmaleimide, ie, N-7 enyl-(2-anilino)succinimide, is produced as a by-product, and the yield of the target phenylmaleimide is low. .
従って本発明は、Ｎ−フェニルマレイミドの製造に際し
、Ｎ−７エニルー（２−アニリノ）スクシンイミド等の
除去困難な不純物の副生を有効に抑制し、目的とするＮ
−フェニルマレイミドの収率を向上せしめることを技術
的課題とする。Therefore, the present invention effectively suppresses by-products of difficult-to-remove impurities such as N-7 enyl-(2-anilino)succinimide during the production of N-phenylmaleimide, and achieves the desired N-phenylmaleimide production.
- The technical problem is to improve the yield of phenylmaleimide.
（問題点を解決するための手段）
本発明は上記技術的課題を達成するために、無水マレイ
ン酸とフェニアミンとを縮合してＮ−フェニルマレイミ
ドを製造するに際して、（Ａ） 各原料物質の仕込み
址が、下記式％式％（１）
式中、Ａは無水マレイン酸の仕込みモル数、ＢＵフェニ
ルアミンの仕込みモル数、
Ｃは酸性触媒の仕込みモル数、
を示す、
を満足する条件下に縮合反応を行なうこと、（Ｂ）
反応終了後、ｐＨが６．５乃至７，５の範囲において反
応系を水洗処理し、残存触媒を抽出除去すること、
という手段を採用するものである。(Means for Solving the Problems) In order to achieve the above-mentioned technical problems, the present invention provides the following steps when producing N-phenylmaleimide by condensing maleic anhydride and phenamine: (A) Preparation of each raw material substance % (1) where A is the number of moles of maleic anhydride charged, the number of moles of BU phenylamine charged, C is the number of moles of acidic catalyst charged, under conditions satisfying the following formula: (B) carrying out a condensation reaction;
After the reaction is completed, the reaction system is washed with water at a pH in the range of 6.5 to 7.5 to extract and remove the remaining catalyst.
（作用）
本発明によれば、各反応物質の仕込み量が上記（１）式
を満足する様な条件下で縮合反応を行なうことによシ、
後述する実施例に示す如く、Ｎ−フェニル−（２−アニ
リノ）スクシンイミド等の除去困難な不純物の副生が有
効に抑制され、これに応じて目的とするＮ−フェニルマ
レイミドノ収率モ顕著に向上するものである。(Function) According to the present invention, by carrying out the condensation reaction under conditions such that the amount of each reactant satisfied the above formula (1),
As shown in the examples below, the by-product of difficult-to-remove impurities such as N-phenyl-(2-anilino)succinimide is effectively suppressed, and the desired yield of N-phenylmaleimide is accordingly significantly increased. It will improve.
即ち、従来の製造法では、無水マレイン酸とフェニルア
ミンとの仕込み量は等モルであったのであるが、用いる
酸性触媒の使用量が極めて夕景であることを考慮すれば
、本発明においては無水マレイン酸の仕込み量がフェニ
ルアミンのそれに対して過剰となっていることが理解さ
れよう。That is, in the conventional production method, the amounts of maleic anhydride and phenylamine charged were equimolar, but considering that the amount of acidic catalyst used is extremely small, in the present invention It will be understood that the amount of maleic acid charged was in excess of that of phenylamine.
従って、本発明によれば仕込んだフェニルアミンの殆ど
全てが目的とする無水マレイン酸との縮合反応に供され
、その結果としてフェニルアミンの副反応に由来するＮ
−フェニル−（２−アニリノ）スクシンイミド等の除去
困難な不純物の発生が有効に抑制されるものである。Therefore, according to the present invention, almost all of the charged phenylamine is subjected to the condensation reaction with the target maleic anhydride, and as a result, N
The generation of impurities that are difficult to remove, such as -phenyl-(2-anilino)succinimide, is effectively suppressed.
また本発明によれば、縮合反応終了後、ｐ）ｆを６．５
乃至７．５、特に６．７乃至７．３の範囲において反応
系を水洗処理して残存触媒を抽出除去することも重要で
ある。Further, according to the present invention, after the condensation reaction, p) f is 6.5
It is also important to wash the reaction system with water in the range of 6.7 to 7.5, especially 6.7 to 7.3, to extract and remove the remaining catalyst.
即ち、上記範囲よシもアルカリ側で水洗処理を行なりと
、生成したＮ−フェニルマレイミドの分解を招き、分離
困難な別の不純物すなわちフマルアニル酸が副生ずると
いう不都合を生じる。また上記範囲よシも酸性側で水洗
処理を行なうと、酸の除去が不十分となり、この酸が引
続いて行なわれる蒸留操作時において蒸留釜内に濃縮し
、Ｎ−フェールマレイミドの重合損失の原因となる。That is, if the water washing treatment is carried out on the alkaline side beyond the above range, the produced N-phenylmaleimide will be decomposed and another impurity that is difficult to separate, namely fumaranilic acid, will be produced as a by-product. Furthermore, if the water washing treatment is carried out on the acidic side beyond the above range, the removal of the acid will be insufficient, and this acid will be concentrated in the distillation pot during the subsequent distillation operation, resulting in a loss of polymerization of N-fermaleimide. Cause.
（作用効果）
かくして本発明によれば、不純物の副生を有効に防止し
、高収率でＮ−フェニルマレイミドを得ることが可能と
なる。(Effects) Thus, according to the present invention, it is possible to effectively prevent the by-product of impurities and obtain N-phenylmaleimide in high yield.
得られたＮ−フェニルマレイミドは、例えば耐熱性熱硬
化性樹脂原料等としての用途に供される。The obtained N-phenylmaleimide is used, for example, as a raw material for a heat-resistant thermosetting resin.
（発明の好適態様）
本発明の製造方法は、無水マレイン酸とフェニルアミン
とを酸性触媒の存在下で縮合せしめ、次いで水洗処理を
行なって残存触媒を抽出除去した後、蒸留分離操作を行
なってＮ−フェニルマレイミドを得るものである。(Preferred Embodiment of the Invention) The production method of the present invention comprises condensing maleic anhydride and phenylamine in the presence of an acidic catalyst, then performing a water washing treatment to extract and remove the remaining catalyst, and then performing a distillation separation operation. N-phenylmaleimide is obtained.
縮合反応工程
縮合反応は、所定の溶媒中に無水マレイン酸、フェニル
アミン及び酸性触媒を溶解乃至分肢せしめ、加熱還流す
ることによシ行なわれる。Condensation Reaction Step The condensation reaction is carried out by dissolving or dissolving maleic anhydride, phenylamine, and an acidic catalyst in a predetermined solvent and heating to reflux.
尚、フェニルアミンとしてはアニリンやトルイジン、ク
ミジン等のｏ−、ｍ＋、或いはｐ−置換アニリンを用い
ることができる。As the phenylamine, aniline, o-, m+, or p-substituted anilines such as toluidine and cumidine can be used.
本発明においては、前述した通シ各原料物質の仕込み量
が、 ／ ＞１．０５を満足する様に−Ｃ
縮合反応を行なうものであるが、特に ／、−ｏ＜１．
２であることが望ましい。（上記式中、Ａ、Ｂ及びＣは
それぞれ無水マレイン酸、フェニルアミン及び酸性触媒
の仕込みモル量を表わす。）即ち、無水マレイン酸の仕
込み童があま）に過剰となると、その回収ロス等により
実施上望ましくない。In the present invention, the -C condensation reaction is carried out such that the amount of each of the raw materials mentioned above satisfies / > 1.05, especially /, -o < 1.
2 is desirable. (In the above formula, A, B, and C represent the molar amounts of maleic anhydride, phenylamine, and acidic catalyst, respectively.) In other words, if the amount of maleic anhydride used is excessive, the recovery loss, etc. Undesirable in practice.
ま九用いる酸性触媒の量は、無水マレイン酸とＮ−フェ
ニルアミンとの合計に当た！＋０．５乃至５重ｉチの範
囲にあることが好ましい。触媒量が０．５重量％よシも
少量である場合には所望の触媒効果が得られず、また５
重盆チよシも多く用い念としても一定以上の効果が得ら
れず、経済的に不利となるばかシか残存触媒の除去が面
倒となるという不都合を生じる。The amount of acidic catalyst used corresponds to the total amount of maleic anhydride and N-phenylamine! It is preferably in the range of +0.5 to 5 times. If the amount of catalyst is as small as 0.5% by weight, the desired catalytic effect cannot be obtained;
Even if the catalyst is used frequently, it is not possible to obtain any effect beyond a certain level, and there are disadvantages in that it is economically disadvantageous and the removal of the remaining catalyst becomes troublesome.
酸性触媒としては、硫酸、塩酸、リン酸等の無機酸やｐ
−トルエンスルホン酸等の有機酸を用いることができる
が、これらはフェニルアミンとの塩の形態となってもよ
い。Examples of acidic catalysts include inorganic acids such as sulfuric acid, hydrochloric acid, and phosphoric acid;
- Organic acids such as toluenesulfonic acid can be used, but these may also be in the form of salts with phenylamine.
加熱還流は、無水マレイン酸、フェニルアミン及び酸性
触媒を溶媒中に溶解乃至分散せしめた後に行なうが、無
水マレイン酸と酸性触媒とを溶媒中に溶解乃至分散させ
之液を加熱還流し、この系にフェニルアミンを溶媒中に
溶解乃至分散させた液を滴下させる様な方法を採っても
よい。Heating and refluxing is performed after dissolving or dispersing maleic anhydride, phenylamine, and an acidic catalyst in a solvent. Alternatively, a method may be adopted in which a solution in which phenylamine is dissolved or dispersed in a solvent is dropped.
溶媒量は一般に、各原料物質の合計量の２乃至１０倍、
特に４乃至６倍であることが好適である。The amount of solvent is generally 2 to 10 times the total amount of each raw material,
In particular, it is preferably 4 to 6 times.
溶媒としては、沸点が！２０℃乃至１８０℃の炭化水素
、ハロダン化炭化水素、及びその他罪プロトン性の極性
溶媒を用いることができる。As a solvent, the boiling point! Hydrocarbons, halodanized hydrocarbons, and other protic polar solvents having a temperature of 20° C. to 180° C. can be used.
反応温度は、通常１００乃至１８０℃、特に１２０°０
乃至１６０″Ｃの範囲にあ夛、圧力は常圧乃至は減圧が
好適である。The reaction temperature is usually 100 to 180°C, especially 120°C.
The temperature is preferably in the range of 160''C to 160''C, and the pressure is preferably normal pressure to reduced pressure.
また反応時間は、一般に２乃至１０時間、特に５乃至６
時間の範囲にある。The reaction time is generally 2 to 10 hours, particularly 5 to 6 hours.
within the time range.
水洗処理工程 縮合反応完了後、この反応系を水洗処理に賦する。Water washing process After the condensation reaction is completed, the reaction system is subjected to water washing treatment.
この水洗処理は、ｐＨ６，５乃至７．５、特に６．７乃
至７．３の範囲の水系を上記反応系に循環供給すること
によシ、残存酸性触媒及び余剰の未反応無水マレイン酸
を抽出除去するものである。This water washing treatment removes the residual acidic catalyst and excess unreacted maleic anhydride by circulating and supplying an aqueous system with a pH range of 6.5 to 7.5, particularly 6.7 to 7.3, to the reaction system. It is extracted and removed.
循環供給に従って、この水系のｐＨに徐々に上昇するた
め、適宜Ｎａ ２ Ｃ０３等のアルカリを添加してｐＨ
コントロールが行なわれる。この場合、循環液中におけ
るＮａ２ＳＯ４等の塩の蓄積濃度は１５〜２０重量％で
あることが望ましい。As the pH of the aqueous system gradually increases as the supply circulates, alkali such as Na 2 C03 is added as needed to adjust the pH.
control is carried out. In this case, the accumulated concentration of salts such as Na2SO4 in the circulating fluid is preferably 15 to 20% by weight.
水洗処理後、Ｎ−フェニルマレイミドを含有する油相は
蒸留操作に賦され、溶媒等が分離され、目的とするＮ−
フェニルマレイミドが得られる。After washing with water, the oil phase containing N-phenylmaleimide is subjected to a distillation operation to separate the solvent, etc., and obtain the desired N-phenylmaleimide.
Phenylmaleimide is obtained.
本発明においては、各原料物質の仕込み量が一定条件を
満足する様に調整されていることから、Ｎ−フェニル−
（２−アニリノ）スクシンイミド等の蒸留分離困難な物
質の副生が有効に抑制されているため、蒸留操作により
容易に目的とするＮ−フェニルマレイミドを得ることが
できる。In the present invention, since the amount of each raw material is adjusted to satisfy certain conditions, N-phenyl-
Since the by-product of substances difficult to separate by distillation, such as (2-anilino)succinimide, is effectively suppressed, the desired N-phenylmaleimide can be easily obtained by distillation.
例えば、後述する実施例からも明らかな通シ、本発明の
製造方法によれば、目的とするＮ−フェニルマレイミド
の収率は９０モルチ以上であシ、極めて高率であること
が理解されよう。ここで、Ｎ−７ヱニルマレイミドの収
率は装入されたアニリン曾を基準として表わした値であ
る。For example, as is clear from the Examples described later, it will be understood that according to the production method of the present invention, the yield of the target N-phenylmaleimide is 90 mole or more, which is an extremely high yield. . Here, the yield of N-7 enylmaleimide is a value expressed based on the charged aniline.
尚、上記蒸留分離に隙しては、蒸留すべき油相中に重合
防止剤を添加し、Ｎ−フェニルマレイミドの重合損失を
防止することが好適である。In addition, during the above-mentioned distillation separation, it is preferable to add a polymerization inhibitor to the oil phase to be distilled to prevent polymerization loss of N-phenylmaleimide.
用いる重合防止剤としては、２，５−ジｔｅｒｔ−ブチ
ルハイドロキノン、４−ｔｅｒｔ−ブチルカテコール等
のそれ自体公知のものをそれ自体公知の量で使用するこ
とができる。As the polymerization inhibitor used, those known per se such as 2,5-di-tert-butylhydroquinone and 4-tert-butylcatechol can be used in known amounts.
実施例１
熱水マレイン酸５１．５９ （０，５２５モル）、硫酸
２．５９ （０，０２６モル）および混合キシレン４０
０ｇを攪拌機、濾過テ斗、還流冷却器、水分離器を備え
た１を丸底フラスコに仕込んだ。フラスコ内容物の加熱
を始め、溶媒の還流が始まった所で、滴下Ｐ斗に別に調
製したアニリン４６．５ ｇ（Ｑ、 ５モル）を混合キ
ミレン１００ｇに溶かした溶液の滴下を開始した。約６
時間かけて滴下し、滴下終了後に後反応を３０分間行っ
た。アニリン溶液を滴下している間に反応で生成した水
の留出が見られた。水分離器に溜った全生成水の量は９
．１９であっ次。全反応終了後、反応混合物に含まれる
溶媒不溶物を戸別した。不溶物量は約３．３ｇであり次
。この不溶物を除いて得た反応生成溶液を抽出中和装置
に導いた。抽出中和装置は原料槽、原料供給ポンプ、回
転円盤型向流抽出機（抽出機液ホールドアツプ３００ｒ
ｎｔ、実段数６段）、ｐＨコントローラー付中和槽及び
水相循環ポンプから構成されている。Example 1 Hydrothermal maleic acid 51.59 (0,525 mol), sulfuric acid 2.59 (0,026 mol) and mixed xylene 40
0 g was charged into a round bottom flask equipped with a stirrer, a filter funnel, a reflux condenser, and a water separator. When the contents of the flask began to be heated and the solvent began to reflux, a separately prepared solution of 46.5 g (Q, 5 mol) of aniline dissolved in 100 g of mixed chymilene was added dropwise to the dropping tube. about 6
The mixture was added dropwise over a period of time, and after the completion of the dropwise addition, a post-reaction was performed for 30 minutes. While dropping the aniline solution, distillation of water produced by the reaction was observed. The total amount of produced water accumulated in the water separator is 9
．． Next time at 19. After completion of all reactions, the solvent-insoluble substances contained in the reaction mixture were separated from each other. The amount of insoluble matter is approximately 3.3g. The reaction product solution obtained by removing the insoluble matter was led to an extraction neutralization device. The extraction neutralization equipment consists of a raw material tank, a raw material supply pump, a rotating disc type countercurrent extractor (extractor liquid hold up 300r
nt, actual number of stages: 6), a neutralization tank with a pH controller, and an aqueous phase circulation pump.
反応生成物溶液を原料槽に仕込み、原料供給ポンプによ
り３００ｍ／／ｈｒの流速で抽出機下部へ供給した。抽
出機の上部へは２０％−Ｎａ ２ Ｓ Ｏ４水溶液（ｐ
Ｈ６，８）を６００ｍ／／ｈｒの流速で供給した。抽出
機円盤を回転させて抽出操作を行わせた。反応生成溶液
に含まれていた酸触媒、未反応のマレイン酸及び無水マ
レイン酸を抽出して排出された水相を中和槽へ導き、１
３％−ＮａＯＨ水溶液にてｐＨ７に中和した。中和した
水相を再び抽出機へ循環させ念。抽出機上部から排出さ
れた生成物の一部を採シ、分液ロウ斗を用いて蒸留水に
よる回分洗浄を行ったが、もはや水相のｐＨに変化は見
られなかった。反応生成物溶液全量を２時間半で処理し
、さらにキシレン１５０ＭＪを送シ込み系内ホールドア
ツプを洗い出した。The reaction product solution was charged into a raw material tank and supplied to the lower part of the extractor at a flow rate of 300 m/hr by a raw material supply pump. A 20%-Na 2 SO 4 aqueous solution (p
H6,8) was supplied at a flow rate of 600 m//hr. The extraction operation was performed by rotating the extractor disk. The acid catalyst, unreacted maleic acid, and maleic anhydride contained in the reaction product solution were extracted, and the discharged aqueous phase was led to a neutralization tank.
It was neutralized to pH 7 with a 3% NaOH aqueous solution. Make sure to circulate the neutralized aqueous phase to the extractor again. A portion of the product discharged from the top of the extractor was collected and washed in batches with distilled water using a separating funnel, but no change was observed in the pH of the aqueous phase. The entire amount of the reaction product solution was treated for two and a half hours, and 150 MJ of xylene was further pumped in to wash out the hold-up in the system.
酸触媒を除去した反応生成溶液に２，４−ジーｔｅｒｔ
−ブチルハイドロキノン０．０９９を添加した後、ロー
タリーエバポレーターにより溶媒のキシレンを留去し、
Ｎ−フェニルマレイミドを主成分とする濃縮物８７．５
１を得た。該濃縮物を蒸留原料とし、分子蒸留装置（神
鋼７アウドラー製）を用い九薄膜蒸留を行った。６Ｍ１
１Ｈｇ、１７０℃（外壁温）の条件下、蒸留々出物８２
．１９を得た。Add 2,4-di-tert to the reaction product solution from which the acid catalyst has been removed.
- After adding 0.099% of butylhydroquinone, the solvent xylene was distilled off using a rotary evaporator,
Concentrate mainly composed of N-phenylmaleimide 87.5
I got 1. Using the concentrate as a raw material for distillation, nine-thin film distillation was performed using a molecular distillation apparatus (Shinko 7 manufactured by Audler). 6M1
Distillate 82 under conditions of 1Hg and 170℃ (outer wall temperature)
．． I got 19.
該留出物を液体クロマトグラフィを用いて分析した結果
、不純物であるＮ−フェニル−（２−アニリノ）スクシ
ンイミドの混入は見られなかった。As a result of analyzing the distillate using liquid chromatography, no contamination with the impurity N-phenyl-(2-anilino)succinimide was found.
Ｎ−フェニルマレイミドの理論生成量に対する総合収率
Ｆｉ９４．９モルチであった。The overall yield Fi was 94.9 mol based on the theoretical amount of N-phenylmaleimide produced.
比較例１
無水マレイン酸とアニリンとの縮合反応において、無水
マレイン酸の仕込み量を４９． Ｏｆｉ （０，５モル
）、滴下するアニリン溶液のアニリンの量を５５、９９
（０，６０モル）とした以外は実施例１と同様に行っ
九。縮合反応終了後、戸別された溶媒不溶物の量は１３
．０．ｌｉ’であった。Comparative Example 1 In the condensation reaction of maleic anhydride and aniline, the amount of maleic anhydride charged was 49. Ofi (0,5 mol), the amount of aniline in the aniline solution to be added dropwise is 55,99
The same procedure as in Example 1 was carried out except that (0.60 mol) was used. After the completion of the condensation reaction, the amount of solvent-insoluble matter separated from door to door was 13
．． 0. It was li'.
最終の蒸留操作で得られた留出物のｆｔｒｘｅｏ、６ｇ
で、この中には不純物であるＮ−フェニル−（２−アニ
リノ）スクシンイミドを０．２％含んでいた。6 g of ftrxeo distillate obtained from the final distillation operation
This contained 0.2% of N-phenyl-(2-anilino)succinimide, an impurity.
理輪生成墓に対するＮ−７工ニルマレイミド総合収率は
７０モルチであっ九。The overall yield of N-7 engineered nilmaleimide for the ring-forming tomb was 70 mol.
比較例２
実施例１と同じ条件下に縮合反応を行って得た反応生成
物溶液を０．５ ％−ＮａＯＨ水溶液によって直接中和
処理した。実施例１と同じ後処理法で最終の蒸留々出物
を得たが、該留出物量は７４．４ｆｉであった。この中
にはＮ −７ｚニル−（２−アニリノ）スクシンイミド
が０．１８ ％含まれていた。Comparative Example 2 A reaction product solution obtained by carrying out a condensation reaction under the same conditions as in Example 1 was directly neutralized with a 0.5% NaOH aqueous solution. The final distillate was obtained using the same work-up method as in Example 1, but the amount of distillate was 74.4 fi. This contained 0.18% of N-7znyl-(2-anilino)succinimide.
Ｎ−フェニルマレイミドの総合収率は８５．８モルチで
あった。The overall yield of N-phenylmaleimide was 85.8 mol.
実施例２
実施例１において、無水マレイン酸の仕込み量を４９．
０．９（０，５０モル）に変更したほかは実施例１と同
様に縮合反応抽出中和を行った。この段階で反応生成物
溶液の液体クロマトグラフィー分析を行った結果、Ｎ−
フェニルマレイミドの収率は９３モルチであっ之〇
該反応生成物溶液に２，５−ジーｔｅｒｔ−ブチルハイ
ドロキノン０．０９，９を添加して溶媒を留去し、濃縮
物８６．５ｇを得た。Example 2 In Example 1, the amount of maleic anhydride charged was changed to 49.
Condensation reaction extraction neutralization was carried out in the same manner as in Example 1 except that the amount was changed to 0.9 (0.50 mol). As a result of liquid chromatography analysis of the reaction product solution at this stage, N-
The yield of phenylmaleimide was 93 mol. 0.09.9 of 2,5-di-tert-butylhydroquinone was added to the reaction product solution, and the solvent was distilled off to obtain 86.5 g of a concentrate. .
該濃縮物を３００ｍ１蒸留フラスコに移し、６詣Ｈｇ、
１４０℃の条件下に単蒸留を行った。濃縮物に残存して
いたキシレンや未反応アニリン等の前留分をカットした
後、Ｎ−フェニルマレイミド主留分を集めた。１時間３
０分かかって得られた主留分は７６．４ｇであった。Ｎ
−フェニルマレイミドの総合収率は８８．３モルチであ
った。Transfer the concentrate to a 300ml distillation flask,
Simple distillation was performed at 140°C. After cutting off the pre-distillate such as xylene and unreacted aniline remaining in the concentrate, the main fraction of N-phenylmaleimide was collected. 1 hour 3
The main fraction obtained after 0 minutes was 76.4 g. N
-The overall yield of phenylmaleimide was 88.3 mol.
比較例３
実施例２において、蒸留原料中に２．５−ジ−ターシャ
リ−ブチルハイドロキノンを添加しなかった外は実施例
２と同様に行った。最終の単蒸留操作で得られた主留分
は６８．３ ｆｌであり、Ｎ−フェニルマレイミドの総
合収率は７９．Ｏモルチであ・りた。Comparative Example 3 The same procedure as in Example 2 was conducted except that 2,5-di-tert-butylhydroquinone was not added to the distillation raw material. The main fraction obtained in the final simple distillation operation was 68.3 fl, and the overall yield of N-phenylmaleimide was 79.3 fl. I did it with Omorchi.
Claims (1)
において縮合反応を行ないＮ−フェニルマレイミドを製
造する方法において、 各原料物質の仕込み量が、下記式、 Ａ／Ｂ−Ｃ≧１．０５ 式中、Ａは無水マレイン酸の仕込みモル数、Ｂはアニリ
ンの仕込みモル数、 Ｃは酸性触媒の仕込みモル数、 を示す、 を満足する様に縮合反応を行ない、反応終了後、ｐＨが
６．５乃至７．５の範囲において反応系を水洗処理し、
残存触媒を抽出除去することを特徴とする製造方法。(1) In a method for producing N-phenylmaleimide by carrying out a condensation reaction of maleic anhydride and aniline in the presence of an acidic catalyst, the amount of each raw material to be charged is determined by the following formula: A/B-C≧1.05 In the formula, A is the number of moles of maleic anhydride charged, B is the number of moles of aniline charged, and C is the number of moles of acidic catalyst charged. The condensation reaction is carried out to satisfy the following, and after the reaction is completed, the pH is 6. The reaction system is washed with water in the range of .5 to 7.5,
A manufacturing method characterized by extracting and removing residual catalyst.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61114777A JPH0686424B2 (en) | 1986-05-21 | 1986-05-21 | Method for producing N-phenylmaleimide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61114777A JPH0686424B2 (en) | 1986-05-21 | 1986-05-21 | Method for producing N-phenylmaleimide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62273952A true JPS62273952A (en) | 1987-11-28 |
| JPH0686424B2 JPH0686424B2 (en) | 1994-11-02 |
Family
ID=14646423
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61114777A Expired - Lifetime JPH0686424B2 (en) | 1986-05-21 | 1986-05-21 | Method for producing N-phenylmaleimide |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0686424B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6383065A (en) * | 1986-09-25 | 1988-04-13 | Nippon Shokubai Kagaku Kogyo Co Ltd | Production of maleimides |
| US4980483A (en) * | 1988-03-25 | 1990-12-25 | Nippon Shokubai Kagaku Kogyo Co., Ltd. | Method for production of maleimides |
| JP2020117538A (en) * | 2020-04-15 | 2020-08-06 | 旭化成ファインケム株式会社 | Manufacturing method of n-cyclohexyl maleimide composition |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3431276A (en) * | 1963-10-25 | 1969-03-04 | Ici Ltd | Process for producing imide derivatives |
| JPS5368770A (en) * | 1976-11-30 | 1978-06-19 | Ihara Chem Ind Co Ltd | Preparation of dicarboxylic acid amide |
| JPS5546394A (en) * | 1978-09-29 | 1980-04-01 | United Technologies Corp | Water collector |
| JPS6011465A (en) * | 1983-06-11 | 1985-01-21 | バイエル・アクチエンゲゼルシヤフト | Manufacture of 1h-pyrrole-2,5-diones |
| JPS60100554A (en) * | 1983-11-05 | 1985-06-04 | K I Kasei Kk | Preparation of n-phenylmaleimide compound |
| JPS615066A (en) * | 1984-06-18 | 1986-01-10 | Nippon Shokubai Kagaku Kogyo Co Ltd | Production of maleimide |
-
1986
- 1986-05-21 JP JP61114777A patent/JPH0686424B2/en not_active Expired - Lifetime
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3431276A (en) * | 1963-10-25 | 1969-03-04 | Ici Ltd | Process for producing imide derivatives |
| JPS5368770A (en) * | 1976-11-30 | 1978-06-19 | Ihara Chem Ind Co Ltd | Preparation of dicarboxylic acid amide |
| JPS5546394A (en) * | 1978-09-29 | 1980-04-01 | United Technologies Corp | Water collector |
| JPS6011465A (en) * | 1983-06-11 | 1985-01-21 | バイエル・アクチエンゲゼルシヤフト | Manufacture of 1h-pyrrole-2,5-diones |
| JPS60100554A (en) * | 1983-11-05 | 1985-06-04 | K I Kasei Kk | Preparation of n-phenylmaleimide compound |
| JPS615066A (en) * | 1984-06-18 | 1986-01-10 | Nippon Shokubai Kagaku Kogyo Co Ltd | Production of maleimide |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6383065A (en) * | 1986-09-25 | 1988-04-13 | Nippon Shokubai Kagaku Kogyo Co Ltd | Production of maleimides |
| JPH0374658B2 (en) * | 1986-09-25 | 1991-11-27 | ||
| US4980483A (en) * | 1988-03-25 | 1990-12-25 | Nippon Shokubai Kagaku Kogyo Co., Ltd. | Method for production of maleimides |
| JP2020117538A (en) * | 2020-04-15 | 2020-08-06 | 旭化成ファインケム株式会社 | Manufacturing method of n-cyclohexyl maleimide composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0686424B2 (en) | 1994-11-02 |
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