JPS6183158A - Preparation of n,n'-m-phenylenebismaleimide - Google Patents

Preparation of n,n'-m-phenylenebismaleimide

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Publication number
JPS6183158A
JPS6183158A JP20435684A JP20435684A JPS6183158A JP S6183158 A JPS6183158 A JP S6183158A JP 20435684 A JP20435684 A JP 20435684A JP 20435684 A JP20435684 A JP 20435684A JP S6183158 A JPS6183158 A JP S6183158A
Authority
JP
Japan
Prior art keywords
phenylenediamine
reaction
maleic anhydride
yield
ketone solvent
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
Application number
JP20435684A
Other languages
Japanese (ja)
Other versions
JPH0655719B2 (en
Inventor
Masahisa Shiotani
塩谷 正久
Manji Sasaki
佐々木 万治
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sumitomo Chemical Co Ltd
Original Assignee
Sumitomo Chemical Co Ltd
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Filing date
Publication date
Application filed by Sumitomo Chemical Co Ltd filed Critical Sumitomo Chemical Co Ltd
Priority to JP59204356A priority Critical patent/JPH0655719B2/en
Publication of JPS6183158A publication Critical patent/JPS6183158A/en
Publication of JPH0655719B2 publication Critical patent/JPH0655719B2/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

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Abstract

PURPOSE:To produce the titled substance in high yield and quality, by reacting m-phenylenediamine with maleic anhydride in a specific amount of a ketone solvent, precipiating the intermediate in the form of crystal, and carrying out the dehydrative cyclization keeping the reaction system in slurry state. CONSTITUTION:m-Phenylenediamine is made to react with maleic anhydride in 3-5 times weight (based on the m-phenylenediamine) of a ketone solvent [(preferably acetone) at 30-60 deg.C to precipitate the N,N'-m-phenylenebismaleamic acid in the form of crystal, and the product is subjected to the dehydrative cyclization reaction in the presence of a dehydration agent (e.g. acetic anhydride) and a catalyst (e.g. an alkaline earth metal compound) keeping the slurry state without converting to a uniform solution. The objective compounf of formula II can be produced by this process. EFFECT:Excellent effect can be achieved by using a tertiary amine as a cocatalyst. USE:Raw material of heat-resistant resin, crosslinking agent, adhesive, etc.

Description

【発明の詳細な説明】 本発明は、耐熱性樹脂、架橋剤および接着剤等の原料と
して需要が増大しているN、N/−m−7二二レンビス
マレイミドの製a方法に関するものである。
DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing N,N/-m-7 2-2lene bismaleimide, which is in increasing demand as a raw material for heat-resistant resins, crosslinking agents, adhesives, etc. be.

N、N′−m−7エニレンピスマレイミドの製造方法と
しては、m−フェニレンジアミンに無水マレイン酸を付
加せしめて、中間体m−7エニレンビスマレアミン酸を
得、次いで、触媒、脱水剤、第三級アミンの存在下にケ
トン系溶媒をm−7二二レンジアミンに対し、7〜9重
量倍と多量使用して反応系を一旦均一溶液にして脱水環
化反応をせしめ、次いで、m−7二二レンジアミンに対
し12〜22重量倍という多量の水を反応マスに添加し
て目的物を沈澱回収するという複雑な方法が知られてい
る(特公昭49−40231号公報および特開昭58−
54648号公報)。
As a method for producing N,N'-m-7 enylene bismaleimide, maleic anhydride is added to m-phenylene diamine to obtain an intermediate m-7 enylene bismaleamic acid, and then a catalyst and dehydration are performed. The reaction system was once made into a homogeneous solution by using a ketone solvent in a large amount of 7 to 9 times the weight of m-7 22-diamine in the presence of a tertiary amine and a dehydration cyclization reaction. A complicated method is known in which a large amount of water, 12 to 22 times the weight of m-7 22-diamine, is added to the reaction mass to precipitate and recover the target product (Japanese Patent Publication No. 49-40231 and Japanese Unexamined Patent Publication No. 1983-
54648).

iN、N’−m−フェニレンビスマレアミン酸N、N’
−m−フェニレンビスマレイミドしかるに、上記公知方
法では目的物であるN、N’−m−7エニレンビスマレ
イミドの反応釜当りの収率が著しく低いという工業的に
極めて大きな欠点を有するのみならず、収率、品質面に
おいても充分満足し得るものではなかった。
iN, N'-m-phenylene bismaleamic acid N, N'
-m-Phenylene Bismaleimide However, the above-mentioned known method not only has an extremely large industrial disadvantage in that the yield per reaction pot of the target product, N,N'-m-7enylene bismaleimide, is extremely low. However, the results were not completely satisfactory in terms of yield and quality.

iたN、N’−m−フェニレンビスマレイミドについて
の実施例は記載されてはいないが、マレイミドの一般的
な合成法として、溶媒を使用しないかあるいは夕景使用
して、マレアミン酸を脱水環化せしめる方法も知られて
いる(特開昭52−125161号公報)。
Although no examples are described for N,N'-m-phenylene bismaleimide, a general method for synthesizing maleimide involves cyclodehydration of maleamic acid without using a solvent or using a sintering method. There is also a known method for causing this (Japanese Unexamined Patent Publication No. 125161/1983).

ところが、上記公知方法では溶媒の使用の有無にかかわ
らず、中間体であるマレアミン酸を沖過などにより系外
に一旦取り出さす必要があり、しかも一旦取出した中間
体を再び脱水剤である酸無水物中に添加し反応系を均一
溶液とした後、加熱して反応を完結せしめるという極め
て複雑な工程をたどる方法であり、工業的には好ましか
らざる煩雑な方法であった。本発明者らはかかる方法に
基ずきN。
However, in the above-mentioned known method, regardless of whether or not a solvent is used, it is necessary to take out the intermediate maleamic acid out of the system by filtration or the like, and the once taken out intermediate is again treated with acid anhydride, which is a dehydrating agent. This method involves an extremely complicated process of adding the compound to a substance to make the reaction system a homogeneous solution, and then heating the reaction system to complete the reaction, which is a complicated process that is not suitable for industrial use. Based on such a method, the present inventors made N.

N′−m−フェニレンビスマレアミン酸を用い、浴媒と
して液体反応体に対して30重量%のアセトンを使用し
て反応を試みた結果、約シ、のN、N’ −m−フェニ
レンビスマレアミン酸を添加した時点で攪拌が困難とな
り、かかる公知方法も、N、N’−m−フェニレンビス
マレイミドの工業的な方法とは言い難いものであった。
A reaction was attempted using N'-m-phenylenebismaleamic acid and 30% by weight of acetone relative to the liquid reactants as a bath medium, resulting in approximately Stirring became difficult upon addition of maleamic acid, and this known method could hardly be called an industrial method for producing N,N'-m-phenylene bismaleimide.

以上のように、いずれの公知方法もN、N/−m−7二
二レンビスマレイミドの工業的な製造方法としては満足
できるものではなく、より生産性が高くより操作が容易
で、しかも高収率で高品位の目的物が得られる工業的に
優れた製造方法の出現が望まれていた。
As mentioned above, none of the known methods is satisfactory as an industrial method for producing N,N/-m-7 2-2lene bismaleimide. It has been desired to develop an industrially superior manufacturing method that can provide high-quality target products in high yield.

本発名者らは、前述の欠点を改良すべく、鋭意検討を重
ねた結果、ケトン系溶媒を特定量用いて付加工程、脱水
工程ともに反応系を均一溶液にすることなり、一貫して
スラリー状態を保ったまま反応せしめることにより、公
知方法の欠点をことごとく改善できることを見い出し本
発明を完成した。
In order to improve the above-mentioned shortcomings, the inventors of the present invention have conducted intensive studies and have decided to use a specific amount of a ketone solvent to make the reaction system a homogeneous solution in both the addition process and the dehydration process. The present invention was completed by discovering that all the drawbacks of known methods can be improved by allowing the reaction to occur while maintaining the state.

すなわち本発明はm−フェニレンジアミンと無水マレイ
ン酸からN 、N’ −m−フェニレンビスマレイミド
を製造するにあたり、ケトン系溶媒をm−フェニレンジ
アミンに対シ3−61量倍使用して、中間体であるN、
N’−m−フェニレンビスマレアミンe ヲ結晶トして
一旦析出せしめ、次の脱水環化工程においても反応系を
均一溶液にすることな(、一貫してスラリー状態を保っ
たまま脱水剤、触媒、第三級アミンの存在下に反応せし
めることを特徴とするN、N’ −m−フェニレンビス
マレイミドの製造方法を提供するものである。
That is, in the present invention, when producing N,N'-m-phenylene bismaleimide from m-phenylene diamine and maleic anhydride, the ketone solvent is used in an amount of 3 to 61 times the amount of m-phenylene diamine to prepare the intermediate. N, which is
N'-m-phenylenebismaleamine e is crystallized and precipitated once, and the reaction system is not made into a homogeneous solution even in the next dehydration cyclization process (the dehydrating agent, The present invention provides a method for producing N,N'-m-phenylene bismaleimide, which is characterized in that the reaction is carried out in the presence of a catalyst and a tertiary amine.

本発明によれば、公知方法に較べ、目的物の収率、品質
ともに優れた結果が得られるのみならず、工業的規模で
の生産において重要な因子となる反応釜当りの収量も著
しく向上する。
According to the present invention, it is possible to not only obtain superior results in both the yield and quality of the target product as compared to known methods, but also to significantly improve the yield per reaction vessel, which is an important factor in production on an industrial scale. .

また、反応終了後ただちに沖過するのみで目的物が高収
率が得られ、公知方法では使用が不可欠であった沈澱剤
としての多量の水が全く不要となった。この結果、沖過
により得られた目的物の乾燥効率が向上するのみならず
、戸液から溶媒を回収する工程も極めて簡素化され、加
えて溶媒回収率に副生じ公知技術の問題点の一つとされ
ていた重金属を含有した多量の廃水の処理も不要となっ
た。
In addition, a high yield of the target product can be obtained by simply filtering immediately after the completion of the reaction, and a large amount of water as a precipitant, which is indispensable in known methods, is completely unnecessary. As a result, not only the drying efficiency of the target material obtained by filtration is improved, but also the process of recovering the solvent from the liquid is extremely simplified, and in addition, the solvent recovery rate is reduced, which is one of the problems of known techniques. It is no longer necessary to treat large amounts of wastewater containing heavy metals, which was thought to be a problem.

以上のように本発明は公知技術の問題点がことごとく改
善された工業的に極めて有用なN、N’−m−7二二レ
ンピスマレイミドの製造方法を提供するものである。
As described above, the present invention provides an industrially extremely useful method for producing N,N'-m-7 2-2lene pismaleimide, which has all the problems of known techniques improved.

本発明で使用されるケトン系溶媒としては、アセトン、
メチルエチルケトン、メチルイソプロピルケトン、メチ
ルイソブチルケトンなどがあげられるが、なかでもアセ
トンが好ましく使用される。その使用量はm−フェニレ
ンジアミンに対し、3〜6重量倍、好ましくは3.5〜
5.5倍使用されるが、溶媒使用量が3重量倍未満であ
るとm−フェニレンジアミンと無水マレイン酸の付加中
間体であるN。
The ketone solvent used in the present invention includes acetone,
Examples include methyl ethyl ketone, methyl isopropyl ketone, and methyl isobutyl ketone, among which acetone is preferably used. The amount used is 3 to 6 times by weight, preferably 3.5 to 6 times the weight of m-phenylenediamine.
If the amount of solvent used is less than 3 times by weight, N, which is an addition intermediate between m-phenylenediamine and maleic anhydride, is used.

N’ −m−7二二レンビスマレアミン岐の結晶が析出
した際に攪拌が困難になり、付加反応が完結しにくくな
る。
When N'-m-7 22lenebismaleamine branch crystals precipitate, stirring becomes difficult and the addition reaction becomes difficult to complete.

一方ケトン系溶媒がm−フェニレンジアミンに対し6重
社倍を越えた場合は、脱水環化反応終了後、そのまま沖
過すると、収率が低下するため、沈澱剤としての水の添
加が必要となり、反応釜当りの収量が低下し、かつ品質
も低下するので好ましくない。
On the other hand, if the amount of ketone solvent exceeds 6 times the amount of m-phenylenediamine, if it is filtered as is after the dehydration cyclization reaction, the yield will decrease and it will be necessary to add water as a precipitant. This is not preferable because the yield per reaction pot and the quality also deteriorate.

また中間体であるN、N’ −m−フェニレンビスマレ
アミン酸は上記ケトン系溶媒の存在下にm−フェニレン
ジアミンと無水マレイン酸とを反応せしめることにより
スラリー状態で得られるが、無水マレイン酸はm−フェ
ニレンジアミンに対し通常215〜2.4モル倍使用さ
れ、反応温度は通常30〜60℃である。
Further, the intermediate N,N'-m-phenylenebismaleamic acid can be obtained in a slurry state by reacting m-phenylenediamine and maleic anhydride in the presence of the above ketone solvent, but maleic anhydride is usually used in an amount of 215 to 2.4 moles relative to m-phenylenediamine, and the reaction temperature is usually 30 to 60°C.

本発明ではかかるN、N’ −m−フェニレンビスマレ
アミン酸のスラリー液に触媒、第三級アミン、脱水剤を
加え脱水環化せしめて目的物を生成させるが、この工程
においては、反応系を均一溶液にすると収率および品質
が低下するので一貫してスラリー状態を保ったまま反応
せしめることが肝要である。
In the present invention, a catalyst, a tertiary amine, and a dehydrating agent are added to the slurry liquid of N,N'-m-phenylene bismaleamic acid to cause dehydration and cyclization to produce the target product. If it is made into a homogeneous solution, the yield and quality will decrease, so it is important to carry out the reaction while maintaining the slurry state throughout.

また本発明に用いられる脱水剤としては、通常、無水酢
酸、無水プロピオン酸等の低級脂肪族カルボン酸無水物
が使用されるが、最も好ましくは無水酢酸であり、低級
脂肪族カルボン酸無水物の使用量は特に制限はないが、
m−フェニレンジアミンに対して通常2.05〜8.0
モル倍使用される。脱水環化工程の反応温度は通常80
〜50℃である。
As the dehydrating agent used in the present invention, lower aliphatic carboxylic anhydrides such as acetic anhydride and propionic anhydride are usually used, but acetic anhydride is most preferred; There is no particular limit to the amount used, but
Usually 2.05 to 8.0 for m-phenylenediamine
Molar times used. The reaction temperature of the dehydration cyclization step is usually 80°C.
~50°C.

本発明に用いられる脱水環化の触媒としては特に制約は
ないが、例えば酸化カルシュラム、酢酸バリウム、酢酸
マグネシュウムなどのアルカリ土類金属化合物、酢酸ニ
ッケル、ニッケルアセチルアセトナートなどの可溶性ニ
ッケル化合物、酢酸コバルト、ナフテン酸コバルトなど
のコバルト系化合物等が挙げられ、その使用量は通常m
−フェニレンジアミンに対し0.002〜0.02モル
である。
There are no particular restrictions on the dehydration cyclization catalyst used in the present invention, but examples include alkaline earth metal compounds such as calcilum oxide, barium acetate, and magnesium acetate, soluble nickel compounds such as nickel acetate and nickel acetylacetonate, and cobalt acetate. , cobalt-based compounds such as cobalt naphthenate, etc., and the amount used is usually m
- 0.002 to 0.02 mol based on phenylenediamine.

さらに、本発明を実施する場合、脱水触媒の存在下に第
三級アミンを助触媒として特定最使用すると、極めて優
れた効果が得られる。
Furthermore, when carrying out the present invention, extremely excellent effects can be obtained by specifically using a tertiary amine as a co-catalyst in the presence of a dehydration catalyst.

その使用量は出発原料であるm−フェニレンジアミンに
対し0.O1〜0.2モル倍、より好ましくは0.05
〜O,18モル倍である。0.2モル倍より多く使用す
ると、反応が急激に進行するためか、反応温度の制御が
困難となり、目的物の品質が低下するのみならず収率も
低下するので好ましくない。一方第三級アミンの使用量
が0.01モル音より少ない場合は、反応が遅くなる傾
向があるので好ましくない。
The amount used is 0.0% based on the starting material m-phenylenediamine. O1 to 0.2 times by mole, more preferably 0.05
~O, 18 mole times. If more than 0.2 molar amount is used, it is not preferable because the reaction proceeds rapidly, making it difficult to control the reaction temperature, resulting in not only a decrease in the quality of the target product but also a decrease in yield. On the other hand, if the amount of tertiary amine used is less than 0.01 mol, the reaction tends to be slow, which is not preferable.

本発明で使用する第三級アミンの種類については特に限
定されないが、トリエチルアミン、トリブチルアミンな
どのトリアルキルアミン、N、N−ジメチルベンジルア
ミン、N、N−ジエチルベンジルアミンなどのN、N−
ジアルキルベンジルアミンが用いられる。
The type of tertiary amine used in the present invention is not particularly limited, but includes trialkylamines such as triethylamine and tributylamine, N,N-
Dialkylbenzylamines are used.

以下本発明を実施例により具体的に説明する。 反応釜
当りの収量は下式にて算出した。
The present invention will be specifically explained below using examples. The yield per reaction pot was calculated using the following formula.

反応釜当りの収量 ただし密度は下記の値を用いた。Yield per reaction pot However, the following values were used for the density.

アセトン=0.79.無水マレイン酸=1m −フェニ
レンジアミン=1゜ トリエチルアミン=0.78.触媒=1゜無水酢酸−i
、os、水=1   “ 実施例 l a拌m付フラスコにアセトンl15.5P’(2,6重
量倍/m−)二二しンジ、アミン)に無水マレイン酸8
9.8?(0,916モル)を溶解させた後、あらかじ
め調整したアセトン82.5 t (1,9重量倍/m
−フェニレンジアミン)とm−フェニレンジアミン44
.5f(0,412モル)とからなる溶液を48℃〜4
50の温度を保ちながら加えた。滴下とともに淡黄色の
N、N’=m−フェニレンビスマレアミン酸が結晶とし
て析出した。滴下終了後さらに同温度で30分攪拌した
後、トリエチルアミン6f (0,059モル)および酢酸ニッケル但)4水相物0
.gr(0,008モル)を加え、さらに無水酢酸LO
1,3f(0,’992モル)を加え、38〜40℃の
温度を保ちながら、スラリー状態下で4時間反応させた
Acetone = 0.79. Maleic anhydride=1m-phenylenediamine=1°triethylamine=0.78. Catalyst = 1゜acetic anhydride-i
, os, water = 1 "Example 1 acetone in a flask with stirring m 15.5P' (2,6 times the weight/m-)
9.8? After dissolving (0,916 mol), 82.5 t of acetone (1,9 times the weight/m
-phenylenediamine) and m-phenylenediamine 44
.. A solution consisting of 5f (0,412 mol) was heated at 48°C to 4
The mixture was added while maintaining the temperature at 50°C. Pale yellow N,N'=m-phenylene bismaleamic acid was precipitated as crystals as the mixture was added dropwise. After the dropwise addition was completed, the mixture was further stirred for 30 minutes at the same temperature, and then triethylamine 6f (0,059 mol) and nickel acetate (4) aqueous phase 0
.. gr (0,008 mol) and further acetic anhydride LO
1,3f (0,992 mol) was added, and the mixture was reacted in a slurry state for 4 hours while maintaining the temperature at 38 to 40°C.

反応終了後室温まで冷却し、結晶を戸別し、301のア
セトンを用いて洗浄を行った後乾燥させて、目的物であ
るN、N’、−m−フェニレンビスマレイミド104.
5fを得た 収率;944% 色相;黄色鮮明。
After the reaction is completed, the crystals are cooled to room temperature, separated, washed with acetone 301, and dried to obtain the target product, N,N',-m-phenylene bismaleimide 104.
5f was obtained. Yield: 944% Hue: Bright yellow.

融点;202.5〜203.5’C反応釜当りの収ff
10.2ty/譚を 実施例 2 アセトンの全使用量を155.5F(8,5重i倍/m
−)二二レンジアミン)、酢酸ニッケル叫4水和物の代
わりに酢酸コバルト[114水和物を0.5F(0,0
02モル)使用する以外は実施例1と同様の操作を行い
、N、N’−m−フェニレンビスマレイミド104、 
l fを得た。 収率;94.8%、色相;黄色鮮明、
融点1202.0〜208.0℃1反応釜当りの収量;
 0.24 f / ml実施例 8 アセトンの全使用量を244.6fC5,5重量倍、、
’m−フェニレンジアミン)、トリエチルアミンを2.
4fC0,028モル)使用する以外は実施例1と同様
の操作を行いN、N’−m−フェニレンビスマレイミド
101.8Fを得た。収率;91.8%1色相;黄色祥
明、融点;201.7〜202.8℃。
Melting point: 202.5-203.5'C Yield per reactor ff
Example 2 The total amount of acetone used was 155.5 F (8.5 times/m
-) 22 diamine), cobalt acetate [114 hydrate instead of nickel acetate tetrahydrate, 0.5F (0,0
The same operation as in Example 1 was carried out except that N,N'-m-phenylene bismaleimide 104,
lf was obtained. Yield: 94.8%, hue: bright yellow,
Melting point: 1202.0-208.0°C Yield per reaction pot;
0.24 f/ml Example 8 The total amount of acetone used was 244.6 fC5.5 times the weight.
'm-phenylenediamine), triethylamine 2.
N,N'-m-phenylene bismaleimide 101.8F was obtained by carrying out the same operation as in Example 1 except that 0.028 mol of N,N'-m-phenylene bismaleimide was used. Yield: 91.8% 1 Hue: Bright yellow, melting point: 201.7-202.8°C.

反応釜当りの収量; 0. l 9 S’ / ml実
施例 4 酢酸ニッケル(II)4水和物の代りに酢酸マグネシュ
ウム0.4F(0,002モル)使用する以外は実施例
1と同様な操作を行いN。
Yield per reaction pot; 0. l 9 S' / ml Example 4 The same procedure as in Example 1 was performed except that 0.4F (0,002 mol) of magnesium acetate was used instead of nickel (II) acetate tetrahydrate.

N’−m−7二二レンビスマレイミド 103.59を得た。収率、93.8%2色相;黄色鮮
明、融点1201.5−208.0℃。
103.59 of N'-m-7 22lene bismaleimide was obtained. Yield, 93.8% 2 hues; bright yellow, melting point 1201.5-208.0°C.

反応釜当りの収量、0.22t/厘l 比較例1 アセトンの全使用量を1oOf(2,2重flt倍/m
−)ニーレンジアミン)とする以外は、実施例1と同様
に付加反応を行った。
Yield per reaction pot, 0.22t/ml Comparative Example 1 The total amount of acetone used was reduced to 1oOf (2.2 flt/m
The addition reaction was carried out in the same manner as in Example 1, except that the addition reaction was carried out in the same manner as in Example 1.

m−フェニレンジアミンのア七トン溶液を約8滴下した
時点で攪拌不能とな9たので反応を中止した。
When about 8 drops of the a7tone solution of m-phenylenediamine were added, stirring became impossible, so the reaction was stopped.

比較例 2 アセトンの全使用量を3109(7重量倍/m−)二二
レンジアミン)とする以外は実施例1と同様な操作を行
いN、NZ−m−フェニレンビスマレイミド 77.9
 fを得た。 収率70,6% 色相;黄色解明融点、
201.5〜20.9.0  反応釜当りの収Urk 
; 0. l 2 t / 14比・?又例 8 実施例1と同様にしてN、NZ −m−フェニレンビス
マレアミン酸のアセトンスラリー欣を得た。次いで内温
48℃下でトリエチルアミンを20.4 t (0,2
t?)加え、さらに酢酸コバルトおよび無水静吸を実施
例2と同盾加えた。
Comparative Example 2 The same operation as in Example 1 was carried out except that the total amount of acetone used was 3109 (7 times the weight/m-) 22-diamine) N,NZ-m-phenylenebismaleimide 77.9
I got f. Yield: 70.6% Hue: Yellow melting point;
201.5~20.9.0 Yield per reaction pot Urk
; 0. l2t/14 ratio・? Example 8 An acetone slurry of N,NZ-m-phenylenebismaleamic acid was obtained in the same manner as in Example 1. Next, 20.4 t (0,2
T? ), and in addition, cobalt acetate and anhydrous aqueous solution were added in the same manner as in Example 2.

無水、、fIf鷹を加えてから約20分後、突然。About 20 minutes after adding anhydrous, fIf hawk, suddenly.

急激な発、猪が起り、アセトンが激しく還流し、反応マ
スも均一浴液になった。氷バスにて急冷した所約lO分
後にアセトンの還流が止んだので、再び内温か38〜4
0℃となる釆バス温をA面し、4時間この温度を保うた
。呆識終了後実施例1と同様の処理を行い、N、N’−
m−フェニレンビスマレイミド95.6fを得た。収率
86.6%、色相;暗黄色、融点1198.5〜201
.5℃、反応釜当りの収量、O,19F/6比較例 4 アセトン全史用量を396F(8,9重量倍/m−−y
エニレンジアミン)以外は実施例1と同様にして、N、
N’ −m−フェニレンビスマレアミン酸スラリー液を
得た。
A sudden explosion occurred, the acetone refluxed violently, and the reaction mass became a homogeneous bath liquid. After quenching in an ice bath, the acetone reflux stopped after about 10 minutes, so the internal temperature dropped again to 38-4.
The pot bath temperature was set to 0°C on side A, and this temperature was maintained for 4 hours. After completing the stupefaction, the same process as in Example 1 is performed, and N, N'-
m-phenylene bismaleimide 95.6f was obtained. Yield 86.6%, hue: dark yellow, melting point 1198.5-201
.. 5°C, yield per reaction pot, O, 19F/6 Comparative Example 4 The total amount of acetone was 396F (8.9 times the weight/m-y
N,
A N'-m-phenylene bismaleamic acid slurry liquid was obtained.

この反応マスに、トリエチルアミン24f(0,237
モル)および酢酸ニッケル(■)4水和物0.8 (0
,003モル)を加え、さらに無水酢酸104.5F(
102モル)を加え、約70℃のバスにて加熱した。内
温は64℃まで上昇し、アセトンが激しく環流し、約2
0分後に反応マスは均一となった。
Triethylamine 24f (0,237
mol) and nickel acetate (■) tetrahydrate 0.8 (0
,003 mol) and then acetic anhydride 104.5F (
102 mol) was added and heated in a bath at about 70°C. The internal temperature rose to 64℃, and acetone refluxed violently, causing a temperature of about 2.
After 0 minutes, the reaction mass became homogeneous.

58〜60℃下で1時間保温した後、水990 yxl
を添加し、析出した結晶を戸別し、990 yglの水
で洗浄を行い乾燥させた。
After keeping warm at 58-60℃ for 1 hour, add 990 yxl of water.
was added, and the precipitated crystals were taken from house to house, washed with 990 ygl of water, and dried.

N、N’−m−フェニレンビスマレイミド95.3Pを
得た。 収率86.8% 色相;黄褐色、 融点;19
8.0〜201.5℃反応釜当りの収量; 0.06 
f / zl上記の結果を表1に示した。
N,N'-m-phenylene bismaleimide 95.3P was obtained. Yield: 86.8% Hue: Yellow-brown, Melting point: 19
8.0-201.5℃ Yield per reaction pot: 0.06
f/zl The above results are shown in Table 1.

Claims (1)

【特許請求の範囲】 1、m−フェニレンジアミンと無水マレイン酸からN,
N′−m−フェニレンビスマレイミドを製造するにあた
り、ケトン系溶媒をm−フェニレンジアミンに対して3
〜6重量倍使用して、中間体であるN,N′−m−フェ
ニレンビスマレアミン酸を結晶として一旦析出せしめ、
次の脱水環化工程においても反応系を均一にすることな
く、一貫してスラリー状態を保ったまま脱水剤、触媒、
第三級アミンの存在下に反応せしめることを特徴とする
N,N′−m−フェニレンビスマレイミドの製造方法。 2、第3級アミンとして、トリエチルアミンをm−フェ
ニレンジアミンに対し、0.05〜0.2モルの範囲で
使用する特許請求の範囲第1項に記載の方法。
[Claims] 1.N from m-phenylenediamine and maleic anhydride,
In producing N'-m-phenylenebismaleimide, the ketone solvent was added to m-phenylenediamine in a ratio of 3
~6 times by weight to once precipitate the intermediate N,N'-m-phenylene bismaleamic acid as crystals,
Even in the next dehydration and cyclization process, the reaction system is kept in a slurry state without making the reaction system homogeneous.
A method for producing N,N'-m-phenylene bismaleimide, which comprises reacting in the presence of a tertiary amine. 2. The method according to claim 1, wherein triethylamine is used as the tertiary amine in an amount of 0.05 to 0.2 mol based on m-phenylenediamine.
JP59204356A 1984-09-28 1984-09-28 Method for producing N, N'-m-phenylene bismaleimide Expired - Fee Related JPH0655719B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP59204356A JPH0655719B2 (en) 1984-09-28 1984-09-28 Method for producing N, N'-m-phenylene bismaleimide

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP59204356A JPH0655719B2 (en) 1984-09-28 1984-09-28 Method for producing N, N'-m-phenylene bismaleimide

Publications (2)

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JPS6183158A true JPS6183158A (en) 1986-04-26
JPH0655719B2 JPH0655719B2 (en) 1994-07-27

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101805280A (en) * 2009-02-18 2010-08-18 咸阳三精科工贸有限公司 Preparation method of N,N'-m-phenylenebismaleimide
JP6273389B1 (en) * 2017-02-03 2018-01-31 ケイ・アイ化成株式会社 Method for producing N-aliphatic substituted maleimide compound
JP6336192B1 (en) * 2017-11-22 2018-06-06 ケイ・アイ化成株式会社 Process for producing aliphatic maleimide

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102531993A (en) * 2011-12-28 2012-07-04 河南省华鼎高分子合成树脂有限公司 Synthetic method of N, N'-m-phenylenedimaleimide

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5353648A (en) * 1976-05-05 1978-05-16 Du Pont Preparation method of maleimide and dimaleimide
JPS5517317A (en) * 1978-07-24 1980-02-06 Mitsui Toatsu Chem Inc Preparation of polymaleimide

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5353648A (en) * 1976-05-05 1978-05-16 Du Pont Preparation method of maleimide and dimaleimide
JPS5517317A (en) * 1978-07-24 1980-02-06 Mitsui Toatsu Chem Inc Preparation of polymaleimide

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101805280A (en) * 2009-02-18 2010-08-18 咸阳三精科工贸有限公司 Preparation method of N,N'-m-phenylenebismaleimide
JP6273389B1 (en) * 2017-02-03 2018-01-31 ケイ・アイ化成株式会社 Method for producing N-aliphatic substituted maleimide compound
JP2018123112A (en) * 2017-02-03 2018-08-09 ケイ・アイ化成株式会社 Manufacturing method of n-aliphatic substituted maleimide compound
JP6336192B1 (en) * 2017-11-22 2018-06-06 ケイ・アイ化成株式会社 Process for producing aliphatic maleimide
JP2019094293A (en) * 2017-11-22 2019-06-20 ケイ・アイ化成株式会社 Production method of aliphatic maleimide

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