JPH0680631A - Production of unsaturated imide compound - Google Patents
Production of unsaturated imide compoundInfo
- Publication number
- JPH0680631A JPH0680631A JP4236966A JP23696692A JPH0680631A JP H0680631 A JPH0680631 A JP H0680631A JP 4236966 A JP4236966 A JP 4236966A JP 23696692 A JP23696692 A JP 23696692A JP H0680631 A JPH0680631 A JP H0680631A
- Authority
- JP
- Japan
- Prior art keywords
- compound
- less
- unsaturated
- hydrocarbon group
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- Pyrrole Compounds (AREA)
- Indole Compounds (AREA)
Abstract
Description
【0001】[0001]
【産業上の利用分野】本発明は、電気、電子分野での積
層板、封止材料、絶縁材料、また繊維強化複合材料、摺
動材料、成形材料等のポリマーの中間体や原料となる不
飽和イミド化合物の製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is an intermediate or raw material for polymers such as laminated plates, encapsulating materials, insulating materials, and fiber reinforced composite materials, sliding materials, molding materials in the fields of electricity and electronics. The present invention relates to a method for producing a saturated imide compound.
【0002】[0002]
【従来の技術】従来、汎用のビスマレイミド系熱硬化性
樹脂として4,4’−ジフェニルメタンビスマレイミド
が知られている(米国特許第2444536号、同特許
第2467835号等)。この化合物の硬化物は耐熱性
に優れる反面、脆く、吸湿性が高いという欠点を有す
る。また汎用の有機溶媒への溶解度も低く、積層板等を
作成する際のワニスの調製が困難である。化合物自体の
融点が高くかつ融点と硬化開始温度が接近しているため
作業性に劣り、硬化物としてその性能を十分発揮させる
のは困難であった。これらの欠点を解決するため、その
後主鎖骨格をジフェニルメタン以外の骨格に置き換えた
様々な不飽和イミドが数多く提案されている(例えば特
開昭63−162706号公報、特開昭60−1566
69号公報等)。2. Description of the Related Art Conventionally, 4,4'-diphenylmethane bismaleimide has been known as a general-purpose bismaleimide thermosetting resin (US Pat. No. 2,444,536, US Pat. No. 2,467,835). The cured product of this compound is excellent in heat resistance, but is fragile and has high hygroscopicity. Further, the solubility in a general-purpose organic solvent is low, and it is difficult to prepare a varnish when producing a laminated plate or the like. Since the compound itself has a high melting point and the melting point and the curing start temperature are close to each other, workability is poor, and it is difficult to sufficiently exhibit its performance as a cured product. In order to solve these drawbacks, various unsaturated imides in which the main chain skeleton is replaced with a skeleton other than diphenylmethane have been proposed thereafter (for example, JP-A-63-162706 and JP-A-60-1566).
69 publication).
【0003】[0003]
【発明が解決しようとする課題】不飽和イミド化合物を
製造する一般的な方法として、芳香族アミン溶液と無水
マレイン酸等の酸無水物溶液とを反応させた後、脱水剤
を作用させる方法が公知である(Org.Synt
h.,41,93(1961)等)。上記の提案された
不飽和イミド化合物は4,4’−ジフェニルメタンビス
マレイミドよりも優れた性能を持つ反面、その製造面に
おいて上記の公知の製造法を応用しようとしても困難を
ともなう場合がある。すなわち、これらの不飽和イミド
はジフェニルメタン以外の剛直な構造を主鎖骨格に導入
していることが原因で、対応する原料ポリアミン化合物
の一般反応溶媒に対する溶解度が小さい場合が多く、そ
のような溶媒を使って反応を行うと、反応一回当たりの
得量は当然小さくなる。この様に原料ポリアミン化合物
が一般反応溶媒に溶けにくい場合はそれらの化合物に適
した良溶媒を併用することで反応一回当たりの得量が小
さくなることを未然に防ぐのが一般的な方法である。し
かしながら、溶解度の大きい溶媒を併用することで製品
の結晶化が妨げられ、通常なら析出した結晶を濾過する
だけで済むところが、反応終了後に反応混合物へ貧溶媒
を加える等の操作がさらに必要となる。また、反応溶媒
を多成分系にすることで脱水剤の分離回収や溶媒リサイ
クル工程も煩雑、困難となる。As a general method for producing an unsaturated imide compound, there is a method of reacting an aromatic amine solution with an acid anhydride solution such as maleic anhydride, and then reacting with a dehydrating agent. Known (Org. Synt
h. , 41, 93 (1961)). While the above-mentioned proposed unsaturated imide compound has superior performance to 4,4'-diphenylmethane bismaleimide, it may be difficult to apply the above-mentioned known production method to the production side. That is, these unsaturated imides often have a low solubility in the general reaction solvent of the corresponding raw material polyamine compound due to the introduction of a rigid structure other than diphenylmethane into the main chain skeleton. When the reaction is carried out using this, the yield per reaction is naturally small. When the raw material polyamine compound is difficult to dissolve in the general reaction solvent as described above, it is a general method to prevent the yield per reaction from decreasing by using a good solvent suitable for those compounds in combination. is there. However, the crystallization of the product is hindered by using a solvent having a high solubility, and normally, it is only necessary to filter the precipitated crystals, but after the completion of the reaction, an operation such as adding a poor solvent to the reaction mixture is further required. . Also, by using a multi-component reaction solvent, the steps of separating and recovering the dehydrating agent and the solvent recycling step become complicated and difficult.
【0004】本発明の目的は上記の様な状況を鑑み、一
般反応溶媒に対する溶解度の低いポリアミン化合物と不
飽和ジカルボン酸無水物とを反応させ、生成したポリア
ミド酸化合物に脱水剤を作用させて閉環して不飽和イミ
ド化合物を製造する方法において、反応一回当たりの製
品得量が大きく、簡便な工程で効率の良い製造方法を提
供することにある。In view of the above situation, an object of the present invention is to react a polyamine compound having a low solubility in a general reaction solvent with an unsaturated dicarboxylic acid anhydride, and act a dehydrating agent on the produced polyamic acid compound to effect ring closure. In the method for producing an unsaturated imide compound by using the above method, a large amount of product can be obtained per reaction, and an efficient production method can be provided by simple steps.
【0005】[0005]
【課題を解決するための手段】本発明者らは、上記目的
を解決するため鋭意検討を重ねた結果、不飽和イミド化
合物を合成する際、エチレン性不飽和二重結合を有する
不飽和ジカルボン酸無水物を反応溶媒に溶かした溶液に
対しポリアミン化合物を実質的に溶液として希釈するこ
となく徐々に連続または分割して仕込み、続いて脱水剤
を反応混合物へ添加する方法により、反応一回当たりの
得量を下げることなく目的の不飽和イミド化合物を製造
できることを見い出した。The inventors of the present invention have conducted extensive studies to solve the above-mentioned object, and as a result, when synthesizing an unsaturated imide compound, an unsaturated dicarboxylic acid having an ethylenically unsaturated double bond is produced. The polyamine compound was added to the solution of the anhydride in the reaction solvent as a solution in a substantially continuous or divided manner without diluting the solution, and then a dehydrating agent was added to the reaction mixture. It has been found that the target unsaturated imide compound can be produced without lowering the yield.
【0006】即ち本発明は、反応溶媒中で、その反応溶
媒に対する25℃での溶解度が50(溶液100g中の
溶質のグラム数、以下同じ)未満で一分子中に少なくと
も二個以上のベンゼン環と二個以上のアミノ基を含むポ
リアミン化合物をエチレン性不飽和二重結合を有する不
飽和ジカルボン酸無水物と反応させ、生成したポリアミ
ド酸化合物に脱水剤を作用させて閉環して不飽和イミド
系化合物を製造する際、その不飽和ジカルボン酸無水物
をその反応溶媒に溶かした溶液にそのポリアミン化合物
を実質的に溶液として希釈しないで徐々に連続または分
割添加して反応させ、生成したポリアミド酸化合物を脱
水剤を作用させて閉環することを特徴とする不飽和イミ
ド化合物の製造方法である。That is, according to the present invention, the solubility in the reaction solvent at 25 ° C. in the reaction solvent is less than 50 (the number of grams of solute in 100 g of the solution, the same applies below), and at least two or more benzene rings are contained in one molecule. And a polyamine compound containing two or more amino groups are reacted with an unsaturated dicarboxylic acid anhydride having an ethylenically unsaturated double bond, and a dehydrating agent is allowed to act on the produced polyamic acid compound to effect ring closure to form an unsaturated imide system. When the compound is produced, the polyamine compound is not diluted with the solution obtained by dissolving the unsaturated dicarboxylic acid anhydride in the reaction solvent, and the polyamine compound is gradually or continuously added and reacted to produce a polyamic acid compound. The method for producing an unsaturated imide compound is characterized in that the ring is closed by acting a dehydrating agent.
【0007】本発明で用いられるポリアミン化合物はそ
こで使用しようとする反応溶媒に対する25℃での溶解
度が50未満で一分子中に少なくとも二個以上のベンゼ
ン環と二個以上のアミノ基を含むものである。その溶解
度が50以上のものは、その反応に本発明方法を採用す
る意義が薄い。具体的には、次に例示されるようなポリ
アミン化合物の中で上記溶解度を有するものである。す
なわち、ジアミン化合物としては、2,2’−ビス〔4
−(4−アミノチオフェノキシ)フェニル〕プロパン、
4,4’−ビス(4−アミノフェノキシ)ベンゾフェノ
ン、The polyamine compound used in the present invention has a solubility of less than 50 at 25 ° C. in a reaction solvent to be used therein and contains at least two or more benzene rings and two or more amino groups in one molecule. When the solubility is 50 or more, the significance of adopting the method of the present invention for the reaction is small. Specifically, it has the above-mentioned solubility among the polyamine compounds exemplified below. That is, as the diamine compound, 2,2′-bis [4
-(4-aminothiophenoxy) phenyl] propane,
4,4′-bis (4-aminophenoxy) benzophenone,
【0008】一般式(1)General formula (1)
【化6】 (式中、R1 、R2 、R3 、R4 はそれぞれハロゲン原
子、または炭素数1〜6の炭化水素基を表し、aとbは
それぞれ0以上4以下の数でa+b≦4を満たし、cと
dはそれぞれ0以上3以下の整数である。二つのアミノ
基の結合位置は酸素原子の結合位置に対しそれぞれオル
ソ、メタ、パラのいずれかを示す。)で表される化合
物、[Chemical 6] (In the formula, R 1 , R 2 , R 3 , and R 4 each represent a halogen atom or a hydrocarbon group having 1 to 6 carbon atoms, and a and b each are a number of 0 or more and 4 or less and satisfy a + b ≦ 4. , C and d are each an integer of 0 or more and 3 or less. The compound represented by the bonding position of the two amino groups is ortho, meta or para with respect to the bonding position of the oxygen atom.
【0009】一般式(2)General formula (2)
【化7】 (式中、R1 、R2 、R3 、R4 はそれぞれハロゲン原
子、または炭素数1〜6の炭化水素基を表し、aとbは
それぞれ0以上4以下の整数でa+b≦4を満たし、c
とdはそれぞれ0以上3以下の整数である。二つのアミ
ノ基の結合位置は酸素原子の結合位置に対しそれぞれオ
ルソ、メタ、パラのいずれかを示す。)で表される化合
物、[Chemical 7] (In the formula, R 1 , R 2 , R 3 , and R 4 each represent a halogen atom or a hydrocarbon group having 1 to 6 carbon atoms, and a and b each are an integer of 0 or more and 4 or less and satisfy a + b ≦ 4. , C
And d are integers of 0 or more and 3 or less. The bonding positions of the two amino groups are either ortho, meta or para with respect to the bonding position of the oxygen atom. ) A compound represented by
【0010】一般式(3)General formula (3)
【化8】 (式中、R1 、R2 、Rf はそれぞれハロゲン原子、ま
たは炭素数1〜6の炭化水素基を表し、a、b、cはそ
れぞれ0以上4以下の整数を表し、b+c≦4を満た
す。二つのアミノ基の結合位置は酸素原子の結合位置に
対しそれぞれオルソ、メタ、パラのいずれかを示す。)
で表される化合物、[Chemical 8] (In the formula, R 1 , R 2 , and R f each represent a halogen atom or a hydrocarbon group having 1 to 6 carbon atoms, a, b, and c each represent an integer of 0 or more and 4 or less, and b + c ≦ 4 is satisfied. The bond positions of the two amino groups are either ortho, meta, or para with respect to the bond position of the oxygen atom.)
A compound represented by
【0011】一般式(4)General formula (4)
【化9】 (式中、R1 、R2 、R3 、R4 、Rf はそれぞれハロ
ゲン原子、炭素数1〜6の炭化水素基、または炭素数1
〜6の含ハロゲン炭化水素基を表し、R5 、R 6 はそれ
ぞれ水素原子、炭素数1〜6の炭化水素基または炭素数
1〜6の含ハロゲン炭化水素基を表す。a、b、c、
d、eは0以上4以下の整数を表し、b+c≦4、d+
e≦4を満たす。二つのアミノ基の結合位置は酸素原子
の結合位置に対しそれぞれオルソ、メタ、パラのいずれ
かを示す。)で表される化合物、[Chemical 9](In the formula, R1, R2, R3, RFour, RfAre each halo
Gen atom, hydrocarbon group having 1 to 6 carbon atoms, or 1 carbon atom
Represents a halogen-containing hydrocarbon group of ~ 6, RFive, R 6Is it
Hydrogen atom, hydrocarbon group having 1 to 6 carbon atoms or carbon atom, respectively
It represents a halogen-containing hydrocarbon group of 1 to 6. a, b, c,
d and e represent an integer of 0 or more and 4 or less, b + c ≦ 4, d +
e ≦ 4 is satisfied. The bonding position of the two amino groups is an oxygen atom
Ortho, meta, or para to the binding position of
Indicates ) A compound represented by
【0012】一般式(5)General formula (5)
【化10】 (式中、R1 、R2 、R3 、R4 、Rf はそれぞれハロ
ゲン原子、炭素数1〜6の炭化水素基、または炭素数1
〜6の含ハロゲン炭化水素基を表し、a、b、c、d、
eは0以上4以下の整数を表し、b+c≦4、d+e≦
4を満たす。二つのアミノ基の結合位置は酸素原子の結
合位置に対しそれぞれオルソ、メタ、パラのいずれかを
示す。)で表される化合物等があげられる。[Chemical 10] (In the formula, R 1 , R 2 , R 3 , R 4 , and R f are each a halogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or 1 carbon atom.
And represents a halogen-containing hydrocarbon group of a to b, a, b, c, d,
e represents an integer of 0 or more and 4 or less, b + c ≦ 4, d + e ≦
4 is satisfied. The bonding positions of the two amino groups are either ortho, meta or para with respect to the bonding position of the oxygen atom. ) And the like.
【0013】一般式(1)において、R1 〜R4 のハロ
ゲン原子としては塩素、臭素、フッ素、ヨウ素;炭素数
1〜6の炭化水素基としてはメチル、エチル、プロピ
ル,ブチル、ペンチル、ヘキシルの各基があげられる。
一般式(1)で表されるナフタレン環含有ジアミン化合
物を具体的に例示すると2,7−ビス(4,4’−アミ
ノフェノキシ)ナフタレン、2,7−ビス(3,3’−
アミノフェノキシ)ナフタレン、2,7−ビス(3,
4’−アミノフェノキシ)ナフタレン等があげられる。In the general formula (1), the halogen atom represented by R 1 to R 4 is chlorine, bromine, fluorine or iodine; and the hydrocarbon group having 1 to 6 carbon atoms is methyl, ethyl, propyl, butyl, pentyl or hexyl. Each group of.
Specific examples of the naphthalene ring-containing diamine compound represented by the general formula (1) include 2,7-bis (4,4′-aminophenoxy) naphthalene and 2,7-bis (3,3′-).
Aminophenoxy) naphthalene, 2,7-bis (3,3
4'-aminophenoxy) naphthalene and the like.
【0014】一般式(2)において、R1 〜R4 のハロ
ゲン原子としては塩素、臭素、フッ素、ヨウ素;炭素数
1〜6の炭化水素基としてはメチル、エチル、プロピ
ル、ブチル、ペンチル、ヘキシルの各基があげられる。
一般式(2)で表されるナフタレン環含有ジアミン化合
物を具体的に例示すると、これらに1,6−ビス(4,
4’−アミノフェノキシ)ナフタレン、1,6−ビス
(3,3’−アミノフェノキシ)ナフタレン、1,6−
ビス(3,4’−アミノフェノキシ)ナフタレン等があ
げられる。In the general formula (2), the halogen atom of R 1 to R 4 is chlorine, bromine, fluorine or iodine; and the hydrocarbon group having 1 to 6 carbon atoms is methyl, ethyl, propyl, butyl, pentyl or hexyl. Each group of.
Specific examples of the naphthalene ring-containing diamine compound represented by the general formula (2) include 1,6-bis (4,4)
4'-aminophenoxy) naphthalene, 1,6-bis (3,3'-aminophenoxy) naphthalene, 1,6-
Examples thereof include bis (3,4′-aminophenoxy) naphthalene.
【0015】一般式(3)おいて、R1 、R2 、Rf の
ハロゲン原子としては、塩素、臭素、フッ素、ヨウ素;
炭素数1〜6の炭化水素基としてはメチル、エチル、プ
ロピル、ブチル、ペンチル、ヘキシルの各基があげられ
る。一般式(3)で表されるベンゼン環含有エーテルジ
アミン化合物を具体的に例示すると1,3−ビス(4,
4’−アミノフェノキシ)ベンゼン、1,3−ビス
(3,3’−アミノフェノキシ)ベンゼン、1,4−ビ
ス(4,4’−アミノフェノキシ)ベンゼン、1,4−
ビス(3,3’−アミノフェノキシ)ベンゼン等があげ
られる。In the general formula (3), the halogen atom represented by R 1 , R 2 and R f is chlorine, bromine, fluorine or iodine;
Examples of the hydrocarbon group having 1 to 6 carbon atoms include methyl, ethyl, propyl, butyl, pentyl and hexyl groups. Specific examples of the benzene ring-containing etherdiamine compound represented by the general formula (3) include 1,3-bis (4,4)
4'-aminophenoxy) benzene, 1,3-bis (3,3'-aminophenoxy) benzene, 1,4-bis (4,4'-aminophenoxy) benzene, 1,4-
Examples thereof include bis (3,3′-aminophenoxy) benzene.
【0016】一般式(4)において、R1 〜R6 、Rf
のハロゲン原子としては塩素、臭素フッ素、ヨウ素;炭
素数1〜6の炭化水素基としてはメチル、エチル、プロ
ピル、ブチル、ペンチル、ヘキシルの各基;炭素数1〜
6の含ハロゲン炭化水素基としては、前記炭化水素基の
水素の少なくとも一部をハロゲン原子で置換したものが
あげられる。一般式(4)で表されるジアミン化合物を
具体的に例示すると、2,2−ビス〔4−(4−アミノ
フェノキシ)フェニル〕メタン、2,2−ビス〔4−
(4−アミノフェノキシ)フェニル〕プロパン、2,2
−ビス〔4−(3−アミノフェノキシ)フェニル〕プロ
パン、2,2−ビス〔3−メチル−4−(アミノフェノ
キシ)フェニル〕プロパン、2,2−ビス〔4−(4−
アミノフェノキシ)フェニル〕プロパン、1,1,1,
3,3,3−ヘキサフルオロ−2,2−ビス〔4−トリ
フルオロメチル−4−(アミノフェノキシ)フェニル〕
プロパン、1,1,1,3,3,3−ヘキサフルオロ−
2,2−ビス〔4−(4−アミノフェノキシ)フェニ
ル〕プロパン等があげられる。In the general formula (4), R 1 to R 6 and R f
The halogen atom of is chlorine, bromine fluorine, iodine; the hydrocarbon group having 1 to 6 carbon atoms is methyl, ethyl, propyl, butyl, pentyl, or hexyl group;
Examples of the halogen-containing hydrocarbon group of 6 include those in which at least a part of hydrogen of the hydrocarbon group is substituted with a halogen atom. Specific examples of the diamine compound represented by the general formula (4) include 2,2-bis [4- (4-aminophenoxy) phenyl] methane and 2,2-bis [4-
(4-Aminophenoxy) phenyl] propane, 2,2
-Bis [4- (3-aminophenoxy) phenyl] propane, 2,2-bis [3-methyl-4- (aminophenoxy) phenyl] propane, 2,2-bis [4- (4-
Aminophenoxy) phenyl] propane, 1,1,1,
3,3,3-Hexafluoro-2,2-bis [4-trifluoromethyl-4- (aminophenoxy) phenyl]
Propane, 1,1,1,3,3,3-hexafluoro-
2,2-bis [4- (4-aminophenoxy) phenyl] propane and the like can be mentioned.
【0017】一般式(5)において、R1 〜R4 、Rf
のハロゲン原子としては塩素、臭素、フッ素、ヨウ素;
炭素数1〜6の炭化水素基としてはメチル、エチル、プ
ロピル、ブチル、ペンチル、ヘキシルの各基;炭素数1
〜6の含ハロゲン炭化水素基としては、前記炭化水素基
の水素の少なくとも一部をハロゲン原子で置換したもの
があげられる。一般式(5)で表されるジアミン化合物
を具体的に例示すると4,4’−ビス(4−アミノフェ
ノキシ)ビフェニル、4,4’−ビス(3−アミノフェ
ノキシ)ビフェニル、4,4’−ビス(4−アミノフェ
ノキシ)−3,3’,5,5’−テトラメチルビフェニ
ル、4,4’−ビス(3−アミノフェノキシ)−3,
3’,5,5’−テトラメチルビフェニル等があげられ
る。また、アミノ基を2つ以上有するその他の化合物と
しては、1,1−ビス〔4−(4−アミノフェノキシ)
フェニル〕シクロヘキサン、1−フェニル−1,1−ビ
ス〔4−(4−アミノフェノキシ)フェニル〕メタン、
トリス〔4−(4−アミノフェノキシ)フェニル〕メタ
ン、トリス〔4−(3−アミノフェノキシ)フェニル〕
メタン、1,1,1−トリス〔4−(3−アミノフェノ
キシ)フェニル〕エタン、1,3−ビス〔ビス(4−ア
ミノフェニル)メチル〕ベンゼン、1,4−ビス〔ビス
(4−アミノフェニル)メチル〕ベンゼン、1,1,
2,2−テトラ(4−アミノフェニル)エタン等があげ
られる。In the general formula (5), R 1 to R 4 and R f
The halogen atom of is chlorine, bromine, fluorine, iodine;
As the hydrocarbon group having 1 to 6 carbon atoms, methyl, ethyl, propyl, butyl, pentyl and hexyl groups; 1 carbon atom
Examples of the halogen-containing hydrocarbon group of to 6 include those in which at least a part of hydrogen of the hydrocarbon group is substituted with a halogen atom. Specific examples of the diamine compound represented by the general formula (5) include 4,4′-bis (4-aminophenoxy) biphenyl, 4,4′-bis (3-aminophenoxy) biphenyl, 4,4′- Bis (4-aminophenoxy) -3,3 ′, 5,5′-tetramethylbiphenyl, 4,4′-bis (3-aminophenoxy) -3,
3 ', 5,5'-tetramethylbiphenyl and the like can be mentioned. Further, other compounds having two or more amino groups include 1,1-bis [4- (4-aminophenoxy)
Phenyl] cyclohexane, 1-phenyl-1,1-bis [4- (4-aminophenoxy) phenyl] methane,
Tris [4- (4-aminophenoxy) phenyl] methane, Tris [4- (3-aminophenoxy) phenyl]
Methane, 1,1,1-tris [4- (3-aminophenoxy) phenyl] ethane, 1,3-bis [bis (4-aminophenyl) methyl] benzene, 1,4-bis [bis (4-amino) (Phenyl) methyl] benzene, 1,1,
2,2-tetra (4-aminophenyl) ethane and the like can be mentioned.
【0018】本発明において用いられるエチレン性不飽
和二重結合を有する不飽和ジカルボン酸無水物は一般式
(6)The unsaturated dicarboxylic acid anhydride having an ethylenically unsaturated double bond used in the present invention has the general formula (6)
【化11】 (式中、Dは2〜24個の炭素原子を持ち、エチレン性
不飽和二重結合を有する二価の有機基である。)で表さ
れる化合物であり、具体的には、例えば無水マレイン
酸、無水イタコン酸、無水シトラコン酸、無水ジクロロ
マレイン酸、無水ピロシンコン酸、無水テトラヒドロフ
タル酸等、あるいはこれら不飽和カルボン酸無水物とジ
エン類とのDiels−Alder反応物、例えばシク
ロペンタジエン、フラン、テルピネンと無水マレイン酸
との環化付加反応物等の少なくとも一種である。[Chemical 11] (In the formula, D is a divalent organic group having 2 to 24 carbon atoms and having an ethylenically unsaturated double bond.) Specifically, for example, maleic anhydride. Acid, itaconic anhydride, citraconic anhydride, dichloromaleic anhydride, pyrocinconic anhydride, tetrahydrophthalic anhydride, etc., or Diels-Alder reaction products of these unsaturated carboxylic acid anhydrides and dienes, such as cyclopentadiene, furan, It is at least one of cycloaddition reaction products of terpinene and maleic anhydride.
【0019】本発明の不飽和イミド化合物の製造方法
は、第一段階でポリアミン化合物と不飽和ジカルボン酸
無水物とのアミド酸を調製し、続いて第二段階で脱水剤
を作用させ、閉環反応を行い対応する不飽和イミド化合
物を得るものである。In the method for producing an unsaturated imide compound of the present invention, a amide acid of a polyamine compound and an unsaturated dicarboxylic acid anhydride is prepared in the first step, and then a dehydrating agent is allowed to act in the second step to carry out a ring closure reaction. Is carried out to obtain a corresponding unsaturated imide compound.
【0020】第一段階のアミド酸の調製方法は、不飽和
ジカルボン酸無水物の溶液にポリアミン化合物を実質的
に溶液として希釈しないで徐々に連続または分割添加す
る手法を取る。ここで実質的に溶液として希釈しないと
は、溶媒を全く使わない場合、ポリアミン化合物を溶解
度の低い溶媒に分散させる場合等をいう。この時、不飽
和ジカルボン酸無水物はポリアミン化合物のアミノ基1
モルに対し1〜1.5倍モル量を用いることが好まし
い。1倍モルより少ないとアミド酸とならないアミノ基
が残存し、1.5倍モルより多く使用しても特に多く用
いたことによる利点は無く、逆に製品中に未反応不飽和
ジカルボン酸類が混入するので好ましくない。The method of preparing the amic acid in the first step is such that the polyamine compound is added to the solution of the unsaturated dicarboxylic acid anhydride as a solution without being diluted substantially continuously or gradually or in portions. Here, "not substantially diluting as a solution" means a case where no solvent is used, a case where a polyamine compound is dispersed in a solvent having a low solubility, and the like. At this time, the unsaturated dicarboxylic acid anhydride is the amino group 1 of the polyamine compound.
It is preferable to use a molar amount of 1 to 1.5 times the molar amount. If it is less than 1 mol, the amino group that does not become amic acid remains, and even if it is used more than 1.5 mol, there is no advantage due to being used in large amounts, and conversely unreacted unsaturated dicarboxylic acids are mixed in the product. Is not preferred.
【0021】添加方法は連続して仕込んでも分割して仕
込んでもどちらでも良い。添加に要する時間は副反応が
顕著にならない範囲であれば特に制限は無いが、通常
0.5〜6時間程度である。反応温度は通常−20〜1
00℃の範囲で行われ、好ましくは室温〜60℃の範囲
である。温度が低すぎると反応の進行が遅く、高すぎる
とポリマー等の副生成物により目的物の純度が下がる。The addition method may be either continuous charging or divided charging. The time required for addition is not particularly limited as long as the side reaction is not significant, but is usually about 0.5 to 6 hours. Reaction temperature is usually -20 to 1
It is carried out in the range of 00 ° C, preferably in the range of room temperature to 60 ° C. If the temperature is too low, the reaction progresses slowly, and if it is too high, the purity of the target product is lowered due to by-products such as polymers.
【0022】本発明において、不飽和ジカルボン酸無水
物の溶液をつくるのに使われる溶媒としては、アセト
ン、メチルエチルケトン、メチルイソブチルケトン等の
ケトン類、アセトニトリル、ベンゾニトリル等のニトリ
ル類、テトラヒドロフラン、ジオキサン、ジエチルエー
テル等のエーテル類が一般的である。これらの中でもア
セトンが好ましい。これはアセトン中でイミド化反応を
行った時、副生成物の中から目的のイミド化合物が選択
的に沈澱してくるからである。使用される溶媒の量は一
般に不飽和ジカルボン酸無水物とポリアミン化合物との
合計重量に対し1〜10重量倍であり、反応一回当たり
の得量を考慮すると1〜4重量倍が好ましい。反応はポ
リアミン化合物添加終了後、0.5〜4時間程度で終了
する。In the present invention, as the solvent used for preparing the solution of the unsaturated dicarboxylic acid anhydride, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, nitriles such as acetonitrile and benzonitrile, tetrahydrofuran, dioxane, Ethers such as diethyl ether are common. Of these, acetone is preferred. This is because when the imidization reaction is performed in acetone, the target imide compound is selectively precipitated from the by-products. The amount of the solvent used is generally 1 to 10 times by weight the total weight of the unsaturated dicarboxylic acid anhydride and the polyamine compound, and preferably 1 to 4 times by weight in consideration of the yield per reaction. The reaction is completed in about 0.5 to 4 hours after the addition of the polyamine compound is completed.
【0023】続いて第二段階である閉環反応を行い不飽
和イミド化合物を得る手法は、第一段階で調製されたア
ミド酸類を単離することなくそのまま続けて行うことが
できる。The second step, which is a ring-closing reaction to obtain an unsaturated imide compound, can be continued without isolation of the amic acid prepared in the first step.
【0024】反応条件は、米国特許第2444536
号、米国特許第3018292号、米国特許第3018
292号、米国特許第3127414号等の明細書に記
載の公知の方法を応用することができる。使用する脱水
剤は通常酸無水物であるが、この中でも無水酢酸が取扱
い、後処理の容易さ、工業的に容易に入手できること等
から好ましい。使用する量はアミド酸基1モルに対し、
1.05〜2モルを用いる。使用される触媒としてはア
ルカリ土類金属の酸化物、鉄(IIおよびIII)、亜
鉛(II)、ニッケル(II)、マンガン(IIおよび
III)、銅(IおよびII)、またはコバルト(II
およびIII)の硫酸塩、炭酸塩、燐酸塩、酢酸塩等で
あり、好ましくは酢酸ニッケル(II)、酢酸コバルト
(II)、酸化マグネシウムである。これらの触媒は単
独でも十分な性能を発揮するが、二種類以上を併用して
も差し支えない。使用される量はアミド酸基1モルに対
し、0.0005〜0.1モルの範囲である。The reaction conditions are as described in US Pat. No. 2,444,536.
No. 3,018,292, US Pat. No. 3,018
Known methods described in the specifications such as 292 and US Pat. No. 3,127,414 can be applied. The dehydrating agent used is usually an acid anhydride. Among them, acetic anhydride is preferable because it is easy to handle, post-process, and industrially easily available. The amount used is based on 1 mol of amic acid group,
1.05 to 2 mol is used. The catalysts used include oxides of alkaline earth metals, iron (II and III), zinc (II), nickel (II), manganese (II and III), copper (I and II), or cobalt (II).
And III) sulfate, carbonate, phosphate, acetate and the like, preferably nickel (II) acetate, cobalt (II) acetate, and magnesium oxide. These catalysts exhibit sufficient performance even when used alone, but two or more kinds of them may be used in combination. The amount used is in the range of 0.0005 to 0.1 mol per mol of amic acid group.
【0025】使用される塩基はトリエチルアミン、トリ
ブチルアミン等の三級アミン類、酢酸ナトリウム、酢酸
カリウム等のアルカリ金属の酢酸塩類である。使用され
る量はアミド酸基1モルに対し、0.05〜1.0モル
の範囲である。これらの塩基は単独でも十分な性能を発
揮するが、二種類以上を併用しても差し支えない。The bases used are tertiary amines such as triethylamine and tributylamine, and acetates of alkali metals such as sodium acetate and potassium acetate. The amount used is in the range of 0.05 to 1.0 mol with respect to 1 mol of amic acid group. These bases exhibit sufficient performance by themselves, but they may be used in combination of two or more kinds.
【0026】反応方法の一例としては、この方法に限定
されるものではないが、第一段階で製造された対応する
アミド酸類の反応混合物にトリエチルアミンを加え室温
で撹拌した後、酢酸ニッケルと酸化マグネシウムを加え
る。次に窒素気流下、無水酢酸を室温〜60℃の温度範
囲で滴下する。滴下に要する時間は通常0.5〜3時間
程度である。室温〜60℃の温度範囲で保温と撹拌を続
ける。反応時間は通常3〜12時間程度である。反応終
了後、析出した結晶を濾取する。効率よく結晶を得るた
めに反応溶媒を常圧下もしくは減圧下に留去するか、流
動性を損なわない程度に濃縮したり、反応溶液を冷却し
たりする手法を必要に応じて併用しても良い。脱水剤由
来の副反応を抑える目的で溶媒の留去は反応温度を上回
らない温度を設定することが好ましい。An example of the reaction method is not limited to this method, but triethylamine is added to the reaction mixture of the corresponding amic acids prepared in the first step, and the mixture is stirred at room temperature, then nickel acetate and magnesium oxide are added. Add. Next, under a nitrogen stream, acetic anhydride is added dropwise in the temperature range of room temperature to 60 ° C. The time required for dropping is usually about 0.5 to 3 hours. Insulation and stirring are continued in the temperature range of room temperature to 60 ° C. The reaction time is usually about 3 to 12 hours. After completion of the reaction, the precipitated crystals are collected by filtration. In order to obtain crystals efficiently, the reaction solvent may be distilled off under normal pressure or reduced pressure, or the reaction solution may be concentrated or concentrated so as not to impair the fluidity, and the reaction solution may be used in combination as necessary. . For the purpose of suppressing side reactions derived from the dehydrating agent, it is preferable to set the temperature at which the solvent is distilled off so as not to exceed the reaction temperature.
【0027】反応終了後、結晶が溶媒に溶けるため析出
しない場合も有り得る。この場合には反応溶媒を常圧下
もしくは減圧下に留去するか、あるいは流動性を損なわ
ない程度に濃縮された反応混合物を濾過するか、または
反応混合物を水、メタノール等の貧溶媒中に投入するか
もしくは、貧溶媒を反応混合物へ滴下することにより結
晶が得られる。使用する貧溶媒の量は反応に用いた溶媒
の0.5〜20倍量が用いられる。上記の操作で得られ
た結晶を少量のアセトン等の揮発性有機溶媒で洗浄し、
あるいはそうすることなく、水、メタノール等の貧溶媒
による洗浄を行う。続いて結晶を常圧もしくは減圧下に
乾燥させることで目的物を得ることができる。こうして
得られた不飽和イミド化合物は工業原料として十分の純
度を持つが、必要に応じてアルコール系等の溶媒から再
結晶してもよい。本発明方法によって得られる不飽和イ
ミド化合物は、原料ポリアミン化合物のNH2 基を一般
式(7)After the reaction is completed, the crystals may be dissolved in the solvent and may not be precipitated in some cases. In this case, the reaction solvent is distilled off under normal pressure or reduced pressure, or the reaction mixture concentrated so that the fluidity is not impaired is filtered, or the reaction mixture is poured into a poor solvent such as water or methanol. Alternatively, crystals are obtained by adding a poor solvent dropwise to the reaction mixture. The amount of the poor solvent used is 0.5 to 20 times the amount of the solvent used in the reaction. The crystals obtained by the above operation were washed with a small amount of a volatile organic solvent such as acetone,
Alternatively, without doing so, washing with a poor solvent such as water or methanol is performed. Subsequently, the crystals are dried under normal pressure or reduced pressure to obtain the desired product. The unsaturated imide compound thus obtained has a sufficient purity as an industrial raw material, but may be recrystallized from a solvent such as an alcoholic solvent, if necessary. The unsaturated imide compound obtained by the method of the present invention has the NH 2 group of the starting polyamine compound represented by the general formula (7)
【化12】 (式中、Dは一般式(6)の場合と同じ意義をもつ。)
で表される基で置換した形の構造を有している。[Chemical 12] (In the formula, D has the same meaning as in the case of the general formula (6).)
It has a structure in which it is substituted with a group represented by
【0028】[0028]
【実施例】以下に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はない。 実施例1 〔N,N’−4,4’−ビス(4−アミノフェノキシ)
ベンゾフェノンビスマレイミドの合成〕200ミリリッ
トル四ツ口フラスコに無水マレイン酸10.3gとアセ
トン70.2gを仕込み、窒素気流下撹拌して溶解させ
た。室温で4,4’−ビス(4−アミノフェノキシ)ベ
ンゾフェノン19.8gを粉体のまま、10分おきに二
時間で分割添加した。このアミン化合物はアセトンに対
する25℃での溶解度が50未満である。さらに三時間
撹拌を続け反応の終了を確認した(第一段階の反応)。
続いてトリエチルアミン2.4gを加え室温で半時間撹
拌した後、酢酸コバルト10mgと酸化マグネシウム1
00mgを加えた。無水酢酸13.0gを室温で半時間
で滴下した後、室温で反応を続けた(第二段階の反
応)。反応終了後、スラリー状の反応混合物を遠心分離
濾過装置にかけて結晶を濾取した。この結晶を少量のア
セトンで洗浄し、減圧下に加温して乾燥し、淡黄色結晶
を収量22.8g(収率82.1%)で得た。このもの
の物性は次のとおりである。 融点173〜176℃ 質量スペクトルM+ =556 元素分析結果EXAMPLES Examples of the present invention will be shown below, but the present invention is not limited thereto. Example 1 [N, N′-4,4′-bis (4-aminophenoxy)]
Synthesis of Benzophenone Bismaleimide] A 200 ml four-necked flask was charged with 10.3 g of maleic anhydride and 70.2 g of acetone, and dissolved by stirring under a nitrogen stream. At room temperature, 19.8 g of 4,4′-bis (4-aminophenoxy) benzophenone was added as powder in 10 minutes intervals for 2 hours. This amine compound has a solubility in acetone at 25 ° C. of less than 50. The stirring was further continued for 3 hours, and the completion of the reaction was confirmed (first step reaction).
Then, after adding 2.4 g of triethylamine and stirring at room temperature for half an hour, 10 mg of cobalt acetate and 1 part of magnesium oxide were added.
00 mg was added. After 13.0 g of acetic anhydride was added dropwise at room temperature for half an hour, the reaction was continued at room temperature (second step reaction). After the completion of the reaction, the slurry-like reaction mixture was subjected to a centrifugal filtration device to collect crystals by filtration. The crystals were washed with a small amount of acetone, heated under reduced pressure and dried to obtain 22.8 g (yield 82.1%) of pale yellow crystals. The physical properties of this product are as follows. Melting point 173-176 ° C Mass spectrum M + = 556 Elemental analysis result
【表1】 [Table 1]
【0029】実施例2 〔N,N’−2,7−ビス(4,4’−アミノフェノキ
シ)ナフタレンビスマレイミドの合成〕2リットル四ツ
口フラスコに無水マレイン酸157.5gとアセトン9
50.8gを仕込み、窒素気流下撹拌して溶解させた。
温度を室温〜35℃に保ちながら2,7−ビス(4,
4’−アミノフェノキシ)ナフタレン250.0gを粉
体のまま十分おきに二時間で分割添加した。このアミン
化合物はアセトンに対する25℃での溶解度が50未満
である。さらに三時間撹拌を続け反応の終了を確認した
(第一段階の反応)。続いてトリエチルアミン44.3
gを加え室温で半時間撹拌した後、酢酸ニッケル1.5
5gを加え40℃まで昇温した。無水酢酸193.9g
を一時間で滴下した後、同温度で反応を続けた(第二段
階の反応)。反応終了後、反応溶媒を内容物が流動性を
失わない程度に回収した後、スラリーを遠心分離濾過装
置にかけて結晶を濾取した。この結晶を水洗、ついでメ
タノールで洗浄し、減圧下に加温して乾燥し、黄色結晶
を収量359.4g(収率98.0%)で得た。このも
のをメチルセロソルブ/イソプロピルアルコール混合溶
媒から再結晶して得たものの物性は次のとおりである。 融点 184〜186℃ 質量スペクトル M+ =502 元素分析結果Example 2 [Synthesis of N, N'-2,7-bis (4,4'-aminophenoxy) naphthalene bismaleimide] In a 2 liter four-necked flask, 157.5 g of maleic anhydride and 9 of acetone were added.
50.8 g was charged and stirred under a nitrogen stream to dissolve.
Keeping the temperature between room temperature and 35 ° C, 2,7-bis (4,4
250.0 g of 4'-aminophenoxy) naphthalene was dividedly added in powder form every 2 hours while keeping sufficient powder. This amine compound has a solubility in acetone at 25 ° C. of less than 50. The stirring was further continued for 3 hours, and the completion of the reaction was confirmed (first step reaction). Then triethylamine 44.3
g and stirred at room temperature for half an hour, and then nickel acetate 1.5
5 g was added and the temperature was raised to 40 ° C. Acetic anhydride 193.9 g
Was added dropwise for 1 hour, and the reaction was continued at the same temperature (second step reaction). After the completion of the reaction, the reaction solvent was recovered to such an extent that the contents did not lose the fluidity, and the slurry was applied to a centrifugal filtration device to collect crystals by filtration. The crystals were washed with water and then with methanol, heated under reduced pressure and dried to obtain 359.4 g (yield 98.0%) of yellow crystals. The physical properties of the product obtained by recrystallization from a mixed solvent of methyl cellosolve / isopropyl alcohol are as follows. Melting point 184-186 ° C Mass spectrum M + = 502 Elemental analysis result
【表2】 [Table 2]
【0030】実施例3 〔N,N’−1,6−ビス(4,4’−アミノフェノキ
シ)ナフタレンビスマレイミドの合成〕2リットル四ツ
口フラスコに無水マレイン酸157.5gとアセトン9
50.8gを仕込み、窒素気流下撹拌して溶解させた。
温度を室温〜35℃に保ちながら2,7−ビス(4,
4’−アミノフェノキシ)ナフタレン250.0gを粉
体のまま十分おきに二時間で分割添加した。このアミン
化合物はアセトンに対する25℃での溶解度が50未満
である。さらに三時間撹拌を続け反応の終了を確認した
(第一段階の反応)。続いてトリエチルアミン44.3
gを加え室温で半時間撹拌した後、酢酸ニッケル1.5
5gを加え40℃まで昇温した。無水酢酸193.9g
を一時間で滴下した後、同温度で反応を続けた(第二段
階の反応)。40℃に内温を保ち反応を進行させながら
反応溶媒を減圧下に回収した。反応終了後、スラリーを
遠心分離濾過装置にかけて結晶を濾取した。この結晶を
少量のアセトンで洗浄し、減圧下に加温して乾燥し、淡
黄色結晶を収量323.1g(収率88.0%)で得
た。このものをメチルセロソルブ/イソプロピルアルコ
ール混合溶媒から再結晶して得たものの物性が次のとお
りである。 融点 140〜151℃ 質量スペクトルM+ =502 元素分析結果Example 3 [Synthesis of N, N'-1,6-bis (4,4'-aminophenoxy) naphthalene bismaleimide] In a 2 liter four-necked flask, 157.5 g of maleic anhydride and 9 of acetone were added.
50.8 g was charged and stirred under a nitrogen stream to dissolve.
Keeping the temperature between room temperature and 35 ° C, 2,7-bis (4,4
250.0 g of 4'-aminophenoxy) naphthalene was dividedly added in powder form every 2 hours while keeping sufficient powder. This amine compound has a solubility in acetone at 25 ° C. of less than 50. The stirring was further continued for 3 hours, and the completion of the reaction was confirmed (first step reaction). Then triethylamine 44.3
g and stirred at room temperature for half an hour, and then nickel acetate 1.5
5 g was added and the temperature was raised to 40 ° C. Acetic anhydride 193.9 g
Was added dropwise for 1 hour, and the reaction was continued at the same temperature (second step reaction). The reaction solvent was recovered under reduced pressure while maintaining the internal temperature at 40 ° C. and proceeding the reaction. After the completion of the reaction, the slurry was applied to a centrifugal filtration device to collect crystals. The crystals were washed with a small amount of acetone, heated under reduced pressure and dried to obtain 323.1 g (yield 88.0%) of pale yellow crystals. The physical properties of the product obtained by recrystallizing this product from a mixed solvent of methyl cellosolve / isopropyl alcohol are as follows. Melting point 140-151 ° C Mass spectrum M + = 502 Elemental analysis result
【表3】 [Table 3]
【0031】実施例4 〔N,N’−1,3−ビス(3,3’−アミノフェノキ
シ)ベンゼンビスマレイミドの合成〕500ミリリット
ル四ツ口フラスコに無水マレイン酸35.2gとアセト
ン198.8gを仕込み、窒素気流下撹拌して溶解させ
た。室温で1,3−ビス(3,3’−アミノフェノキ
シ)ベンゼン50.0gを粉体のまま十分おきに二時間
で分割添加した。このアミン化合物はアセトンに対する
25℃での溶解度が50未満である。さらに三時間撹拌
を続け反応の終了を確認した(第一段階の反応)。続い
てトリエチルアミン7.8gを加え室温で半時間撹拌し
た後、酢酸コバルト0.033gと酸化マグネシウム
0.33gを加えた。無水酢酸42.4gを室温で一時
間で滴下した後、室温で反応を続けた(第二段階の反
応)。反応終了後、スラリー状の反応混合物を遠心分離
濾過装置にかけて結晶を濾取した。この結晶を少量のア
セトンで洗浄し、減圧下に加温して乾燥し、淡黄色結晶
を収量63.0g(収率81.5%)で得た。このもの
の物性は次のとおりである。 融点 139〜141℃ 質量スペクトルM+ =452 元素分析結果Example 4 [Synthesis of N, N'-1,3-bis (3,3'-aminophenoxy) benzenebismaleimide] 35.2 g of maleic anhydride and 198.8 g of acetone were placed in a 500 ml four-necked flask. Was charged and dissolved under stirring in a nitrogen stream. At room temperature, 50.0 g of 1,3-bis (3,3′-aminophenoxy) benzene was added as powder in two hours in divided portions. This amine compound has a solubility in acetone at 25 ° C. of less than 50. The stirring was further continued for 3 hours, and the completion of the reaction was confirmed (first step reaction). Subsequently, 7.8 g of triethylamine was added and stirred at room temperature for half an hour, and then 0.033 g of cobalt acetate and 0.33 g of magnesium oxide were added. After 42.4 g of acetic anhydride was added dropwise at room temperature for 1 hour, the reaction was continued at room temperature (second step reaction). After the completion of the reaction, the slurry-like reaction mixture was subjected to a centrifugal filtration device to collect crystals by filtration. The crystals were washed with a small amount of acetone, heated under reduced pressure and dried to obtain 63.0 g (yield 81.5%) of pale yellow crystals. The physical properties of this product are as follows. Melting point 139-141 ° C Mass spectrum M + = 452 Elemental analysis result
【表4】 [Table 4]
【0032】実施例5 〔N,N’−2,2−ビス〔4−(4−アミノフェノキ
シ)フェニル〕プロパンビスマレイミドの合成〕1リッ
トル四ツ口フラスコに無水マレイン酸51.5gとアセ
トン453.0gを仕込み、窒素気流下撹拌して溶解さ
せた。温度を室温〜35℃に保ちながら2,2−ビス
〔4−(4−アミノフェノキシ)フェニル〕プロパン1
02.6gを粉体のまま十分おきに二時間で分割添加し
た。このアミン化合物はアセトンに対する25℃での溶
解度が50未満である。さらに三時間撹拌を続け反応の
終了を確認した(第一段階の反応)。続いてトリエチル
アミン15.2gを加え室温で半時間撹拌した後、酢酸
ニッケル0.53gを加え、40℃に昇温した。無水酢
酸66.4gを40℃、一時間で滴下した後、同温度で
反応を続けた(第二段階の反応)。反応終了後、溶媒を
減圧下に留去し、続いてスラリー状の反応混合物を遠心
分離濾過装置にかけて結晶を濾取した。この結晶を水洗
後、メタノールで洗浄し、減圧下に加温して乾燥し、淡
黄色結晶を収量122.7g(収率86.0%)で得
た。このものの物性は次のとおりである。 融点 90〜96℃ 質量スペクトルM+ =570Example 5 [Synthesis of N, N'-2,2-bis [4- (4-aminophenoxy) phenyl] propane bismaleimide] In a 1-liter four-necked flask, 51.5 g of maleic anhydride and 453 of acetone were added. 0.0 g was charged and the mixture was dissolved by stirring under a nitrogen stream. 2,2-bis [4- (4-aminophenoxy) phenyl] propane 1 while maintaining the temperature at room temperature to 35 ° C
02.6 g was dividedly added every 2 hours while keeping the powder as it was. This amine compound has a solubility in acetone at 25 ° C. of less than 50. The stirring was further continued for 3 hours, and the completion of the reaction was confirmed (first step reaction). Subsequently, 15.2 g of triethylamine was added and stirred at room temperature for half an hour, 0.53 g of nickel acetate was added, and the temperature was raised to 40 ° C. After 66.4 g of acetic anhydride was added dropwise at 40 ° C. over 1 hour, the reaction was continued at the same temperature (second step reaction). After completion of the reaction, the solvent was distilled off under reduced pressure, and then the reaction mixture in the form of slurry was applied to a centrifugal separation filtration device to collect crystals by filtration. The crystals were washed with water, washed with methanol, heated under reduced pressure and dried to obtain 122.7 g (yield 86.0%) of pale yellow crystals. The physical properties of this product are as follows. Melting point 90-96 ° C Mass spectrum M + = 570
【表5】 [Table 5]
【0033】実施例6 〔N,N’−4,4’−ビス(3−アミノフェノキシ)
ビフェニルビスマレイミドの合成〕500ミリリットル
四ツ口フラスコに無水マレイン酸35.2gとアセトン
246.3gを仕込み、窒素気流下撹拌して溶解させ
た。室温で4,4’−ビス(3−アミノフェノキシ)ビ
フェニル60.0gを粉体のまま十分おきに二時間で分
割添加した。このアミン化合物はアセトンに対する25
℃での溶解度が50未満である。さらに三時間撹拌を続
け反応の終了を確認した(第一段階の反応)。続いてト
リエチルアミン7.8gを加え室温で半時間撹拌した
後、酢酸コバルト0.033gと酸化マグネシウム0.
33gを加えた。無水酢酸42.4gを室温で一時間で
滴下した後、室温で反応を続けた(第二段階の反応)。
反応終了後、スラリー状の反応混合物を遠心分離濾過装
置にかけて結晶を濾取した。この結晶を少量のアセトン
で洗浄し、減圧下に加温して乾燥し、淡黄色結晶を収量
72.6g(収率84.3%)で得た。このものの物性
は次のとおりである。 融点 206〜209℃ 質量スペクトルM+ =528Example 6 [N, N'-4,4'-bis (3-aminophenoxy)]
Synthesis of Biphenyl Bismaleimide] A 500 ml four-necked flask was charged with 35.2 g of maleic anhydride and 246.3 g of acetone, and dissolved by stirring under a nitrogen stream. At room temperature, 60.0 g of 4,4′-bis (3-aminophenoxy) biphenyl was added as powder in a divided manner over a period of 2 hours. This amine compound is 25 against acetone
Solubility at 0 ° C is less than 50. The stirring was further continued for 3 hours, and the completion of the reaction was confirmed (first step reaction). Subsequently, 7.8 g of triethylamine was added and the mixture was stirred at room temperature for half an hour, then 0.033 g of cobalt acetate and 0.
33 g was added. After 42.4 g of acetic anhydride was added dropwise at room temperature for 1 hour, the reaction was continued at room temperature (second step reaction).
After the completion of the reaction, the slurry-like reaction mixture was subjected to a centrifugal filtration device to collect crystals by filtration. The crystals were washed with a small amount of acetone, heated under reduced pressure and dried to obtain pale yellow crystals in an amount of 72.6 g (yield 84.3%). The physical properties of this product are as follows. Melting point 206-209 ° C. Mass spectrum M + = 528
【表6】 [Table 6]
【0034】[0034]
【発明の効果】本発明の製造方法においては、 (A)原料となるポリアミン化合物を溶媒に溶かす必要
が無いため、溶解工程や特別な溶液保存容器を必要とし
ない。 (B)反応濃度を高く設定できるため反応一回当たりの
得量が大きくなり製造コストの低減が期待できる。 (C)反応濃度を所望の値に選べるため原料ポリアミン
化合物の性質や反応性の違いにより反応条件を柔軟に設
定できる。これは本発明の汎用性の大きいことを意味す
る。 (D)溶媒の使用量が原料の溶解度に左右されないた
め、使用する溶媒量を反応に最適な値に設定でき、使用
溶媒のコスト低減や溶媒回収の時間短縮が可能となる。 (E)製造過程に中間体であるアミド酸類を反応釜から
取り出す必要が無いため、手間や作業時間の短縮、使用
溶媒の節約を図ることができる。 等の利点がある。この様に本発明の製造方法は、性能的
に優れながら一般汎用溶媒への溶解度が低いため、不飽
和イミド化合物への変換が経済的に不利であったポリア
ミン化合物を用いて簡便かつ合理的に不飽和イミド化合
物を調製できる製造方法であり、応用範囲も広く工業的
に優れるものである。INDUSTRIAL APPLICABILITY In the production method of the present invention, since it is not necessary to dissolve (A) the raw material polyamine compound in a solvent, there is no need for a dissolving step or a special solution storage container. (B) Since the reaction concentration can be set to be high, the yield per reaction is increased, and reduction in manufacturing cost can be expected. (C) Since the reaction concentration can be selected to a desired value, the reaction conditions can be flexibly set depending on the properties and reactivity of the raw material polyamine compound. This means that the versatility of the present invention is great. (D) Since the amount of the solvent used does not depend on the solubility of the raw materials, the amount of the solvent used can be set to an optimum value for the reaction, and the cost of the solvent used and the solvent recovery time can be shortened. (E) Since it is not necessary to take out the intermediate amic acid from the reaction vessel in the production process, it is possible to reduce labor and work time, and save solvent used. And so on. As described above, the production method of the present invention is simple and rational using a polyamine compound which is economically disadvantageous in conversion to an unsaturated imide compound because of its low solubility in general-purpose solvents while being excellent in performance. It is a production method capable of preparing an unsaturated imide compound, has a wide range of applications, and is industrially excellent.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 金川 修一 茨城県つくば市北原6 住友化学工業株式 会社内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Shuichi Kanakawa 6 Kitahara, Tsukuba, Ibaraki Prefecture Sumitomo Chemical Co., Ltd.
Claims (8)
℃での溶解度が50(溶液100g中の溶質のグラム
数、以下同じ)未満で一分子中に少なくとも二個以上の
ベンゼン環と二個以上のアミノ基を含むポリアミン化合
物をエチレン性不飽和二重結合を有する不飽和ジカルボ
ン酸無水物と反応させ、生成したポリアミド酸化合物に
脱水剤を作用させて閉環して不飽和イミド系化合物を製
造する際、その不飽和ジカルボン酸無水物をその反応溶
媒に溶かした溶液にそのポリアミン化合物を実質的に溶
液として希釈しないで徐々に連続または分割添加して反
応させ、生成したポリアミド酸化合物に脱水剤を作用さ
せて閉環することを特徴とする不飽和イミド化合物の製
造方法。1. In a reaction solvent, 25 to the reaction solvent
A polyamine compound having a solubility at 50 ° C. of less than 50 (gram of solute in 100 g of solution, the same applies hereinafter) and containing at least two or more benzene rings and two or more amino groups in one molecule is an ethylenically unsaturated double bond. When reacting with an unsaturated dicarboxylic acid anhydride having a bond to produce an unsaturated imide compound by ring closure by acting a dehydrating agent on the resulting polyamic acid compound, the unsaturated dicarboxylic acid anhydride as the reaction solvent An unsaturated imide compound, characterized in that the polyamine compound is gradually or continuously added to the dissolved solution without being diluted as a solution and reacted to cause a polyamic acid compound to react with a dehydrating agent to cause ring closure. Manufacturing method.
子、または炭素数1〜6の炭化水素基を表し、aとbは
それぞれ0以上4以下の数でa+b≦4を満たし、cと
dはそれぞれ0以上3以下の整数である。二つのアミノ
基の結合位置は酸素原子の結合位置に対しそれぞれオル
ソ、メタ、パラのいずれかを示す。)で表される化合物
であって、その反応溶媒に対する25℃での溶解度が5
0未満である請求項1記載の不飽和イミド化合物の製造
方法。2. A polyamine compound represented by the general formula (1): (In the formula, R 1 , R 2 , R 3 , and R 4 each represent a halogen atom or a hydrocarbon group having 1 to 6 carbon atoms, and a and b each are a number of 0 or more and 4 or less and satisfy a + b ≦ 4. , C and d are each an integer of 0 or more and 3 or less. The bonding position of the two amino groups is ortho, meta or para with respect to the bonding position of the oxygen atom). And its solubility in the reaction solvent at 25 ° C is 5
The method for producing an unsaturated imide compound according to claim 1, which is less than 0.
子、または炭素数1〜6の炭化水素基を表し、aとbは
それぞれ0以上4以下の整数でa+b≦4を満たし、c
とdはそれぞれ0以上3以下の整数を表す。二つのアミ
ノ基の結合位置は酸素原子の結合位置に対しそれぞれオ
ルソ、メタ、パラのいずれかを示す。)で表される化合
物であって、その反応溶媒に対する25℃での溶解度が
50未満である請求項1記載の不飽和イミド系化合物の
製造方法。3. A polyamine compound represented by the general formula (2): (In the formula, R 1 , R 2 , R 3 , and R 4 each represent a halogen atom or a hydrocarbon group having 1 to 6 carbon atoms, and a and b each are an integer of 0 or more and 4 or less and satisfy a + b ≦ 4. , C
And d each represent an integer of 0 or more and 3 or less. The bonding positions of the two amino groups are either ortho, meta or para with respect to the bonding position of the oxygen atom. The method for producing an unsaturated imide compound according to claim 1, wherein the compound has a solubility in a reaction solvent at 25 ° C. of less than 50.
たは炭素数1〜6の炭化水素基を表し、a、b、cはそ
れぞれ0以上4以下の整数を表し、b+c≦4を満た
す。二つのアミノ基の結合位置は酸素原子の結合位置に
対しそれぞれオルソ、メタ、パラのいずれかを示す。)
で表される化合物であって、その反応溶媒に対する25
℃での溶解度が50以下である不飽和イミド化合物の製
造方法。4. A polyamine compound represented by the general formula (3): (In the formula, R 1 , R 2 , and R f each represent a halogen atom or a hydrocarbon group having 1 to 6 carbon atoms, a, b, and c each represent an integer of 0 or more and 4 or less, and b + c ≦ 4 is satisfied. The bond positions of the two amino groups are either ortho, meta, or para with respect to the bond position of the oxygen atom.)
A compound represented by
A method for producing an unsaturated imide compound having a solubility at 50 ° C of 50 or less.
ゲン原子、炭素数1〜6の炭化水素基、または炭素数1
〜6の含ハロゲン炭化水素基を表し、R5 、R 6 はそれ
ぞれ水素原子、炭素数1〜6の炭化水素基または炭素数
1〜6の含ハロゲン炭化水素基を表す。a、b、c、
d、eは0以上4以下の整数を表し、b+c≦4、d+
e≦4を満たす。二つのアミノ基の結合位置は酸素原子
の結合位置に対しそれぞれオルソ、メタ、パラのいずれ
かを示す。)で表される化合物であって、その反応溶媒
に対する25℃での溶解度が50未満である不飽和イミ
ド化合物の製造方法。5. A polyamine compound represented by the general formula (4):(In the formula, R1, R2, R3, RFour, RfAre each halo
Gen atom, hydrocarbon group having 1 to 6 carbon atoms, or 1 carbon atom
Represents a halogen-containing hydrocarbon group of ~ 6, RFive, R 6Is it
Hydrogen atom, hydrocarbon group having 1 to 6 carbon atoms or carbon atom, respectively
It represents a halogen-containing hydrocarbon group of 1 to 6. a, b, c,
d and e represent an integer of 0 or more and 4 or less, b + c ≦ 4, d +
e ≦ 4 is satisfied. The bonding position of the two amino groups is an oxygen atom
Ortho, meta, or para to the binding position of
Indicates ) A compound represented by
Unsaturated imidis having a solubility of less than 50 at 25 ° C
A method for producing a compound.
ゲン原子、炭素数1〜6の炭化水素基、または炭素数1
〜6の含ハロゲン炭化水素基を表し、a、b、d、eは
0以上4以下の整数を表し、b+c≦4、d+e≦4を
満たす。二つのアミノ基の結合位置は酸素原子の結合位
置に対しそれぞれオルソ、メタ、パラのいずれかを示
す。)で表される化合物であって、その反応溶媒に対す
る25℃での溶解度が50未満である不飽和イミド化合
物の製造方法。6. A polyamine compound represented by the general formula (5): (In the formula, R 1 , R 2 , R 3 , R 4 , and R f are each a halogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or 1 carbon atom.
To 6 represent a halogen-containing hydrocarbon group, a, b, d and e represent an integer of 0 or more and 4 or less, and satisfy b + c ≦ 4 and d + e ≦ 4. The bonding positions of the two amino groups are either ortho, meta or para with respect to the bonding position of the oxygen atom. ), Which is a compound represented by the formula (1), and has a solubility in a reaction solvent at 25 ° C. of less than 50.
ーテル類からなる群から選ばれた少なくとも1種である
請求項1、2、3、4、5または6記載の製造方法。7. The production method according to claim 1, wherein the reaction solvent is at least one selected from the group consisting of ketones, nitriles and ethers.
3、4、5または6記載の製造方法。8. The reaction solvent is acetone, 1, 2,
The production method according to 3, 4, 5 or 6.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP4236966A JPH0680631A (en) | 1992-09-04 | 1992-09-04 | Production of unsaturated imide compound |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP4236966A JPH0680631A (en) | 1992-09-04 | 1992-09-04 | Production of unsaturated imide compound |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH0680631A true JPH0680631A (en) | 1994-03-22 |
Family
ID=17008409
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP4236966A Pending JPH0680631A (en) | 1992-09-04 | 1992-09-04 | Production of unsaturated imide compound |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH0680631A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107162922A (en) * | 2017-05-24 | 2017-09-15 | 吉林大学 | A kind of diamine monomer of polyimides containing pi-allyl and its polyimide polymer and preparation method |
-
1992
- 1992-09-04 JP JP4236966A patent/JPH0680631A/en active Pending
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107162922A (en) * | 2017-05-24 | 2017-09-15 | 吉林大学 | A kind of diamine monomer of polyimides containing pi-allyl and its polyimide polymer and preparation method |
CN107162922B (en) * | 2017-05-24 | 2020-04-21 | 吉林大学 | Allyl-containing polyimide diamine monomer, polyimide polymer thereof and preparation method |
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