JPH03223248A - Production of unsaturated dicarboxylic acid imide-based compound - Google Patents

Abstract

PURPOSE:To produce the title high purity compound in high purity by subjecting an unsaturated dicarboxylic amide acid compound to ring closure through dehydration using an acid anhydride as a dehydrating agent in the presence of a basic catalyst and a metallic salt catalyst, decomposing an acid as a by-product with an orthoester and removing. CONSTITUTION:An unsaturated dicarboxylic acid amide shown by formula I (D is bifunctional organic group containing at least one carbon-carbon double bond; R<1> is n-functional organic group containing at least one carbon atom; (n) is >=1 integer) suck as those expressed by formula II is subjected to ring closure through dehydration using an acid anhydride such as acetic anhydride as a dehydrating agent in the presence of a basic catalyst (e.g. triethylamine) and a metallic salt catalyst (e.g. cobalt chloride) and an acid prepared as a by-product is decomposed with an orthoester (e.g. orthoformic acid methyl ester) shown by formula III (R<2> and R<3> are organic groups containing at least one carbon atom) into an alcohol and an ester, which are removed to give a high purity unsaturated dicarboxylic acid amic imide-based compound (e.g. compound shown by formula IV) shown by formula III. This compound is useful as a raw material for addition type imide resin.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a new method for producing an unsaturated dicarboxylic acid imide compound used in the production of addition-type imide resins, etc.

[Conventional technology]

One of the methods for producing unsaturated dicarboxylic acid imide compounds used in the production of addition-type imide resins, etc. is a method of ring-closing an unsaturated amic acid compound. One of the methods for ring closure is, for example, the chemical ring closure method described in JP-A-53-23396.

The chemical ring closure method is a method of performing dehydration ring closure using a dehydrating agent such as acetic anhydride. This method has the advantage that the reaction can be carried out at low temperatures and in a short time, so the amount of polymer components contained in the obtained unsaturated dicarboxylic acid imide compound is small, and the purity of the compound is as high as about 90% by weight. be.

[Problem to be solved by the invention]

However, in the chemical ring-closing method, treatment with a dehydrating agent is required after the ring-closing reaction is completed, so water is usually added to the reaction solution to precipitate the reaction product, followed by filtration, water washing, and removal of the by-produced acid. Perform neutralization, etc. These purification steps are very complicated, and there are also problems such as a low yield of unsaturated dicarboxylic acid imide compounds due to (7) zero sulfur during treatment.

This invention was made in view of the above circumstances, and
It is an object of the present invention to provide a manufacturing method capable of obtaining an unsaturated dicarboxylic acid imide compound with high yield and high purity since no complicated purification steps are required.

[Means to solve the problem]

In order to solve the above problems, the method for producing an unsaturated dicarboxylic acid imide compound according to the present invention includes an unsaturated dicarboxylic acid imide compound represented by the following general formula (1), an acid anhydride as a dehydrating agent, a base After dehydration and ring closure in the presence of a metal salt catalyst and a metal salt catalyst, the by-produced acid is expressed by the following general formula (
n) An unsaturated dicarboxylic acid imide compound represented by the following general formula (m) is obtained by decomposing and removing the orthoester represented by R"C-+OR"l, -(II) into alcohol and ester. The purpose is to obtain the following.

[For production]

The expansion water ring closure reaction that occurs when the unsaturated dicarboxylic acid amidic acid compound represented by the general formula (r) is reacted in the presence of an acid anhydride as a dehydrating agent, a basic catalyst, and a metal salt catalyst can be carried out at a low temperature, Since the process can be carried out in a short time, the resulting unsaturated dicarboxylic acid imide compound contains significantly less high molecular weight components and has high purity. In addition, by treating the acid by-produced after the completion of the reaction with the orthoester represented by the general formula (n), the acid is decomposed into alcohol and ester and becomes easier to remove.
Complicated purification steps such as neutralization are no longer necessary, losses during the purification steps are reduced, and the yield of the resulting unsaturated dicarboxylic acid imide compound is increased.

〔Example〕

The present invention will be explained in detail below.

The unsaturated dicarboxylic acid amidic acid compound used in this invention refers to a compound represented by the following general formula (1). However, in the above formula, D represents a few organic groups having at least one carbon-carbon double bond, R1 represents an n-valent organic group containing at least one carbon atom, and n represents one or more Represents an integer. The method of obtaining such an unsaturated dicarboxylic acid amidic acid compound is not particularly limited in the present invention, but for example, the method of obtaining such an unsaturated dicarboxylic acid amidic acid compound is
An unsaturated dicarboxylic acid anhydride represented by the following - general formula...
) with the amine or polyamine preferably in the presence of an organic solvent inert to the reaction system, or by reacting in a solvent-free system.

The unsaturated dicarboxylic acid anhydride represented by the above general formula (a) is not particularly limited, but for example,
maleic anhydride, citraconic anhydride, itaconic anhydride,
Tetrahydrophthalic anhydride, nadic anhydride, and
Examples thereof include halogen-substituted products and alkyl-substituted products. These compounds can be used alone or in combination.

Examples of the amine or polyamine represented by the above general formula (bl) include, but are not limited to, the following compounds. The following compounds can also be used alone or in a mixture of multiple types. .Methylamine, ethylamine, l-propylamine, 1,2-dimethylpropylamine, 3-methoxypropylamine, 3-ethoxypropylamine, 3-propoxypropylamine,
3-isopropoxypropylamine, 3-butoxypropylamine, 3-isobutoxypropylamine, 3-(
2-ethylhexyloxy)propylamine, 3-laurioxybrobylamine, 3-myristyloxypropylamine, methylaminopropylamine, dimethylaminopropylamine, diethylaminopropylamine, dibutylaminopropylamine, 2-hydroxyethylaminopropylamine Bylamine, dimethylaminoethoxypropylamine, laurylaminopropylamine, jetanolaminopropylamine, iminobispropylamine, methylaminobispropylamine, n-butylamine, isobutylamine, 5ec-butylamine, hexylamine, 2-ethylhexylamine, Dodecylamine, cyclohexylamine, arylamine, 3-decycloxyamine, dimethylaminoethylamine, diethylaminoethylamine, ethylaminoethylamine, α-phenethylamine, β-phenethylamine, fafurylamine, methoxyamine, m-aminobenzylamine, metaphenylenediamine , 4-chlormethaphenylenediamine, 5-nitromethaphenylenediamine, 4,6-dimethylmethaphenylenediamine, paraphenylenediamine,
2-Chlorparaphenylenediamine, 2-nitroparaphenylenediamine, 2-cyanoparaphenylenediamine, 2.5-dichlorparaphenylenediamine, 26-cyanoparaphenylenediamine, 2.5-diethylparaphenylenediamine, 5- Chlor-2-methylparaphenylenediamine, tetrafluorophenylenediamine, tolylenediamine, 3,5-diethyl-2,4-tolylenediamine, 2-picolylamine, 3-picolylamine,
4-picolylamine, metaxylylenediamine, paraxylylenediamine, hexamethylenediamine, heptamethylenediamine, 4.4-dimethylhebutamethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, 4 .4'-diaminodiphenylmethane, 3,4'-
Diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 3,3', 4.4'-tetraaminodiphenylmethane, 4,4'-diamino-3,3'-diethyldiphenylmethane, 4,4'-diamino-3,3 ′
-diethyl-5,5'-dimethyldiphenylmethane, 4
．． 4'-bis(p-aminophenoxy)diphenylmethane, 4.4'-bis(m-aminophenoxy)diphenylmethane, 2.2', 3.3'-tetrachlor-4
4'-diaminodiphenylmethane, diaminodicyclohexylmethane, 4.4'-bis(p-aminophenoxy)diphenylmethane, 4.4'-bis(m-aminophenoxy)diphenylethane, t.

2-bis-(3-aminopropoxy)-ethane, 2-aminopropatol, 3-aminopropatol, 1,2-
Diaminopropane, 1.3-diaminopropane, 4.4
'-Diaminodiphenylprono7.3.3'-diaminodiphenylpropane, 1°2-bis-(3-aminopropoxy)-2,2-dimethylpropane, 4.4'-bis(p-aminophenoxy)diphenylpropane , 4.4
'-bis m-aminophenoxy) diphenylpropane,
22-bis(4-aminophenyl)propane, 14-diaminobutane, 1,4-diaminophenyl hexane, bis-(3-aminopropyl)ether, α,ω-bis-(
3-aminopropyl)-ethylene glycol ether, 3.3'-diaminodiphenyl ether, 3.4'
~diaminodiphenyl ether, 4,4'-diaminodiphenyl ether) Lt, 3. 4.4'-) riaminodiphenyl ether, 3.3', 4.4'-tetraamino diphenyl ether, bis(p-βamino-te
rt-butylphenyl)ether, toluidine, 4.4
'-methylenedi-o-) rubidine, 4,4'-methylenedi-6-bromo-2-toluidine, aniline, ethylaniline, dichloroaniline, 4,4'-methylenedi2.
6-dichloroaniline, 4,4'-methylenedi2,6
- Itubroviraniline, isopropoxyaniline, chloroaniline, bromoaniline, iodoaniline, nitroaniline, 4,4'-methylenedi-2,6-dibromoaniline, 4,4'-methylenedi-2-bromo-6-chloroaniline , bis-p-aminophenyl aniline, methylene bis anthraniline acid, methylene bis methyl anthranilate, 3,3'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone,
3.3', 4.4'-tetraaminodiphenylsulfone, p-bis(4-aminophenoxy)diphenylsulfone, p-bis(3-aminophenoxy)diphenylsulfone, 2.2-bis-[4-(4 -aminophenoxy)phenyl]sulfone, orthotolidine sulfone, 4
．． 4'-diaminodiphenyl sulfide, bis=(4-
aminophenyl) disulfide, 3.3', 4.4
'-Tetraaminodiphenyl sulfide, N-aminoethylpiperidine, N-aminoethyl-4-pipecoline, N-aminoethylmorpholine, N-aminopropylpiperidine, N-aminopropyl-2-pipecoline, N-
Aminopropyl-4-pipecoline, N-aminopropylmorpholine, 2-aminoethylpiperidine, 4-aminomethylpiperidine, N-aminopiperidine, ■-amino-4-methylpiperazine, 1,4-bisaminopropylbiperazine, N -aminopropylbiverazine, -amino-4-cyclohexylpiperazine, 2-aminopyrazine, 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, 2.3-diaminopyridine, 2.5-diaminopyridine, 2,6-diaminopyridine, 2,3.
6-) riaminopyridine, 2-amino-3-methylpyridine, 2-amino-4-methylpyridine, 2-amino-
5-methylpyridine, 2-amino-6-methylpyridine, 2-amino-4-ethylpyridine, 2-amino-4-
Propylpyridine, 2-amino-4,6-dimethylpyridine, 2,6-diami2-4-methylpyridine, 2-amino-3-nitropyridine, 2-amino-5-nitropyridine, 2-chloro-4-amino Pyridine, 2-chloro-5-aminopyridine, 2-amino-3,5-dichloropyridine, 4-amino-3,5-dichloropyridine, 2
-amino-3,5-dichloro-6-methylpyridine, 2
-amino-3,5-dichloro-4-methylpyridine, 2
-amino-5-chloro-3-methylpyridine, 2-amino-3,5-dichloro-4,6-dimethylpyridine, 2
．． 4-diaminopyrimidine, 2゜4-diamino-6-(
4-pyridyl)-5-) riazine, p-bis(4-aminophenoxy)benzene, m-bis(4-aminophenoxy)benzene, p-bis(3-aminophenoxy)benzene, m-bis(3-amino phenoxy)benzene,
1.3.5-) riaminobenzene, 4.4'-diamino-3-methoxyazobenzene, 1.5-diaminonaphthalene, 1.3.5-) liaminonaphthalene, 3.3'-
Dimethyl-4,4'-diaminobiphenyl, 4,4'-
Diaminoctafluorobiphenyl, 2,5-diaminoterephthalic acid, 3,4'-diaminobenzanilide, 4
, 4'-diaminobenzanilide, 4-(p-aminophenoxy)-4aminobenzanilide, 3.3'-dimethoxybenzidine, 3.3'-dimethylbenzidine, 3
．． 3'diaminobenzidine, 3.3'-dihydroxybenzidine, 2.2'-dichloro-5,5'-dimethoxybenzidine, 2.2', 5.5'-tetrachlorobenzidine, 2.4-diaminotoluene, 2 .4-bis(
β-amino-tert-butyl)toluene, 4゜4'-
Diaminobenzophenone, polytetramethylene oxide di-p-aminobenzoate, trimethylene bis-(
4-aminophenyl), bis(4-aminophenyl)diphenylsilane, bis(4-aminophenyl)dimethylsilane, bis(4-aminophenyl)phenylphosphine oxide, bis(4-aminophenyl)methylphosphine oxide, melamine, 4.4'-diaminostilbene, 9.9-bis(4-aminophenyl) -
10-1 nitroanthracene, 2. 6-'; Aminoanthraquinone, 1,5-diaminoanthraquinone, 9
．． 9-bis(4-aminophenyl)fluorene, 5-amino-1-(4'-aminophenyl)-1,3,3-trimethylindane, 6-amino-1-(4'-aminophenyl)-1, 3,3 trimethylindane, anisidine, phenetidine, aminophenol, 2-aminothiophenol, 4-aminothiophenol, aminobenzoic acid, 2,5-diaminobenzoic acid, 3,5-diaminobenzoic acid, xylidine, 4.4 '-Methylenedi2゜6-xylidine, 2,6-diamitubenzothiazole, m-aminobenzoic acid hydrazide, 2,4-diaminomesitylene, hexaaminocyclophosphazene, 1.
1-diamino-3゜3.5.5-tetraphenoxycyclophosphazene, 1,3.5-)lis(p-aminophenoxy)-1,3,5-)rifenoxycyclophosphazene, hexakis( p-aminophenoxy)-cyclophosphazene, etc.

The acid anhydride used as a dehydrating agent when dehydrating and ring-closing the unsaturated dicarboxylic acid amide acid compound represented by the general formula (1) is not particularly limited, but includes, for example, acetic anhydride, propionic anhydride, etc. Examples include acids, lower monoalkylcarboxylic acid anhydrides such as butyric anhydride, and the like. These acid anhydrides can be used alone or in combination.

The blending ratio of such an acid anhydride and the unsaturated dicarboxylic amide acid compound represented by the general formula (1) is not particularly limited in the present invention, but the amide acid group in the unsaturated dicarboxylic amide acid compound 1 to 5 acid anhydrides per equivalent
The amount is preferably mol, more preferably 2 to 3 mol.

The basic catalyst used in this invention is not particularly limited, but includes, for example, trialkylamines having an alkyl group having 1 to 10 carbon atoms such as trimethylamine, triethylamine, and trilobylamine; N,N-dimethylbenzylamine; N-methylmorpholine, 1.8-
Examples include diazabicyclo(5,4,0)7-undecene and the like. These can be used alone or in combination.

The blending ratio of such a basic catalyst and the unsaturated dicarboxylic acid amide acid compound represented by the above formula (I) is not particularly limited in the present invention, but the ratio of 1 amide acid group in the unsaturated dicarboxylic acid amide acid compound o, o basic catalyst per equivalent
It is preferable to set it as i-0.5 mol.

Further, the metal salt catalyst used in the present invention is not particularly limited, but includes, for example, cobalt chloride,
Divalent or trivalent cobalt compounds such as cobalt carbonate, cobalt sulfate, and cobalt naphthenate; divalent nickel compounds such as nickel acetate, nickel (acetylacetonate), and nickel carbonate; magnesium chloride, magnesium carbonate, magnesium acetate, and Divalent magnesium compounds such as magnesium chlorate, monomers such as sodium acetate
Examples include sodium compounds of high valence. These can be used alone or in combination.

The blending ratio of such a metal salt catalyst and the unsaturated dicarboxylic acid amide acid compound represented by the above formula (1) is not particularly limited in the present invention, but the ratio of 1 amide acid group in the unsaturated dicarboxylic acid amide acid compound 0.0 per equivalent of metal salt catalyst
It is preferable to set it as 001-0.2 mol.

In this invention, it is necessary to add both the same basic compound and the metal salt compound as a catalyst to the reaction system. This is because the ring-closing reaction of the unsaturated dicarboxylic acid amidic acid compound in the presence of a dehydrating agent is promoted even when only the basic compound is used as a catalyst, but when a basic compound is added to the reaction system, This is because by adding a metal salt compound, the catalytic activity of the basic catalyst is increased, the reaction efficiency is increased, and the reaction proceeds under milder conditions. Note that the metal salt compound itself has poor catalytic activity in the ring-closing reaction. That is, it is thought that the metal salt compound acts as a promoter in this reaction.

The organic solvent used in this invention is not particularly limited, but includes, for example, dimethylformamide, dimethylacetamide, dimethylsulfoxide, N-methylpyrrolidone, acetonitrile, acetone, dioxane, benzene, toluene, xylene, cyclohexane, and methylethylketone. , methyl isobutyl ketone, tetrahydrofuran and the like. These can be used alone or in combination.

The blending ratio of these organic solvents and the unsaturated dicarboxylic acid amide acid compound represented by the above formula (1) is not particularly limited in the present invention, but the unsaturated dicarboxylic acid amide acid compound 1
It is preferable that the amount of the organic solvent is 1.0 to 4.0 parts by weight.

The reaction temperature of the dehydration ring-closing reaction in this invention varies depending on the type and amount of acid anhydride, catalyst and solvent, but is 20 to 1
00°C is preferable, and 40 to 60°C is more preferable.

When the unsaturated dicarboxylic acid amide acid compound represented by formula (1) is dehydrated and ring-closed in the presence of an acid anhydride, a basic catalyst, and a metal salt catalyst as a dehydrating agent, the following formula (
An unsaturated dicarboxylic acid imide compound represented by DI) is obtained.

However, during this reaction, since the acid anhydride is hydrolyzed, acid is produced as a by-product. For example, when the acid anhydride is an alkyl monocarboxylic acid anhydride represented by the following formula (C) R'Co-0-COR' (C), the following formula (d) R' C00)1 ...The alkyl monocarboxylic acid represented by (d) is produced as a by-product.

In this invention, the acid by-produced in this way is decomposed into an alcohol and an ester using an orthoester represented by the following formula (n). For example, if the acid anhydride has the formula (C
In the case of the carboxylic acid anhydride represented by 1, the decomposition reaction by the orthoester is as follows.

R' C0OR” +R” C0OR” +R
” OH The alcohols and esters that are produced when acids are decomposed in this way do not require neutralization, unlike acids.Also, these alcohols and esters usually have much lower boiling points than the acids in question. It is possible to remove it by distillation.In addition, when decomposing the by-product acid with the orthoester, in some cases, in advance,
It is also possible to perform the decomposition after removing some of the acid by distillation or the like.

The orthoester that can be used in this invention is not particularly limited, but includes, for example, orthoformic acid methyl ester,
Examples include ethyl orthoformate, propyl orthoformate, methyl orthoacetate, ethyl orthoacetate, propyl orthoacetate, methyl orthopropionate, ethyl orthopropionate, propyl orthopropionate, and the like. These can be used alone or in combination.

The reaction temperature of such a decomposition reaction using orthoester is more preferably 50 to 130°C.

The amount of the orthoester used is also not particularly limited, but is preferably about 1.0 to 10.0 mol per equivalent of acid.

In addition, in the dehydration ring closure reaction of the unsaturated dicarboxylic acid amide acid compound, the unsaturated dicarboxylic amide acid compound is not isolated from the reaction solution of the unsaturated dicarboxylic acid anhydride and the amine or polyamine, but is added to the reaction solution. The ring-closing reaction can also be carried out by adding a dehydrating agent, a basic catalyst, and a metal salt catalyst. Of course, it goes without saying that the unsaturated dicarboxylic acid amidate compound may be used after being isolated from the reaction solution and pulverized.

As described above, in the method for producing an unsaturated dicarboxylic acid imide compound according to the present invention, after the completion of the ring-closing reaction,
Since the by-produced acid is decomposed into alcohol and ester by the orthoester and removed, complicated purification steps such as neutralization and washing with water can be omitted, and the purification step itself can be made very simple. Therefore, the loss of unsaturated dicarboxylic acid imide compounds during the purification process is reduced, and the yield thereof is increased. In some cases, the produced unsaturated dicarboxylic acid imide compound can be used in the next step without being isolated. In this case, the yield of the unsaturated dicarboxylic acid imide compound is 100%. Further, since the dehydration ring-closing reaction proceeds at a low temperature and is completed in a short time, the purity of the obtained unsaturated dicarboxylic acid imide compound is high.

Therefore, the unsaturated dicarboxylic acid imide compound obtained by the present invention is extremely useful for laminates for printed circuit boards, which require high heat resistance and high purity, and molding materials. When producing a laminate or a molding material, other ingredients are added to the unsaturated dicarboxylic acid imide compound in appropriate proportions as necessary.

In order to produce the above-mentioned laminate etc. using the unsaturated dicarboxylic acid imide compound obtained by the production method of the present invention, it is convenient to use a prepreg impregnated with the unsaturated dicarboxylic acid imide compound.

This prepreg is produced, for example, as follows. That is, a varnish is prepared by dissolving an unsaturated dicarboxylic acid imide compound in a solvent and adding other ingredients in appropriate proportions as necessary, and after impregnating a base material with this varnish, the solvent is evaporated. Prepreg is produced by drying and solidifying the compound, or by semi-curing the same compound. As the varnish, a solution obtained by synthesizing an unsaturated dicarboxylic acid imide compound can be used as it is, or after adding appropriate components. The base material used here is not particularly limited, and for example, inorganic fiber cloth such as glass cloth, quartz fiber cloth, highly heat-resistant fiber cloth such as aromatic polyamide fiber (aramid fiber) cloth, etc. may be used. . These base materials are usually used after surface treatment with a coupling agent or the like. The temperature for semi-curing is 120-250
°C is preferred. If the temperature is higher than this range, molding may become extremely difficult, and if it is lower than this range, the curing reaction may not proceed sufficiently.

The laminate is produced, for example, as follows.

Layer the desired number of prepregs, layer metal foil, circuit-formed inner layer material, etc. as necessary,
A laminate plate is produced by lamination molding. Since this laminate uses an unsaturated dicarboxylic acid imide compound obtained by the manufacturing method according to the present invention, it has the advantage of being highly heat resistant and having excellent adhesive properties and insulation properties. As the metal foil, a foil made of copper, nickel, etc. is used.

More specific examples of the present invention will be described below along with comparative examples, but the invention is not limited to the following examples.

Example 1 - 197 g (0.5 mol) of unsaturated dicarboxylic amic acid having the following structure (compound: N, N'-4,4'-diphenylmethane bismaleamic acid) was dissolved in 394 g of NN-dimethylformamide. , and 127.5 g of acetic anhydride (] as a dehydrating agent).

225 mol, 0 nickel acetate tetrahydrate as metal salt catalyst
．． After adding 2 g (0.001 mol) and 10.1 g (0.1 mol) of triethylamine as a basic catalyst, the reaction was carried out at 60° C. for 1 hour. After the reaction, 20
Cool to °C and add 8 g (0,25 mol) of meta/-
was added to decompose unreacted acetic anhydride into acetic acid and methyl acetate. Next, 135 g (2.25 mol) of methyl orthoacetate was added to the reaction solution as an orthoester, and the mixture was heated at 100° C. for 30 minutes. After heating, the reaction solution was cooled to 20° C. and the amount of acetic acid in the reaction solution was measured using a liquid chromatograph. No peak corresponding to acetic acid was observed.

Next, 500 g of water was added to the reaction solution to precipitate. When this precipitate was filtered and dried, 175 g of N,N'-4,4'-diphenylmethane-bis-maleimide (pale yellow powder, yield 98%) having the following structure was obtained.

Further, the purity of this compound was measured by liquid chromatography and was found to be 90.9%.

Example 2 In Example 1, 10.1 g (0.1 mol) of N-methylmorpholine was used instead of triethylamine as a basic catalyst, and cobalt acetate tetrahydrate was used instead of nickel acetate tetrahydrate as a metal salt catalyst. 0.2g (0,00t mol)
A dehydration ring-closing reaction was carried out in the same manner as in Example 1 except that each of the following was used. After the reaction is completed, the pressure is 20-30
Distillation was carried out for 2 hours at +u+Hg and a temperature of 50-60°C.

After the distillation was completed, the amount of acetic acid remaining in the residue was measured using a liquid chromatograph and found to be 8.95 g (0.15 mol).

Next, 36 g (0.3 mol) of methyl orthoacetate was added to the residue, and the mixture was reacted at 100° C. for 30 minutes. After the reaction was completed, the reaction solution was cooled to 20° C., and the amount of acetic acid in the reaction solution was measured using a liquid chromatograph. No peak corresponding to acetic acid was observed. Next, the reaction solution was heated to a pressure of 20 to 3
When distilled for 1 hour at 0 mmh and a temperature of 50 to 60 °C,
179 g of NN'-4,4'-diphenylmethane-bis-maleimide (pale yellow powder, yield 100%) was obtained. The purity of this unsaturated dicarboxylic acid imide compound was measured by liquid chromatography and found to be 90. It was .5%.

Example 3 191 g (1 mol) of unsaturated dicarboxylic acid amic acid (compounder: N-phenylmaleamic acid) having the following structure was dissolved in 573 g of acetone, and 153 g (1,5 mol) of acetic anhydride was added as a dehydrating agent to this. After adding 0.2 g (0.001 mol) of cobalt naphthenate as a metal salt catalyst and 10.1 g (0.1 mol) of triethylamine as a basic catalyst, the reaction was carried out at 60° C. for 1 hour. After the reaction was completed, the same purification treatment as in Example 1 was carried out, resulting in
171 g of N-phenylmaleimide (
A yield of 99%) was obtained.

Further, the purity of this compound was measured by liquid chromatography and was found to be 91.5%.

- Comparative Example 1 - 194 g (0.5 mol) of N,N'-4,4'-diphenylmethanebismaleamic acid was dissolved in 394 g of N,N-dimethylformamide, and 143 g (143 g) of acetic anhydride was added as a dehydrating agent to this. , 4 mol), 1.26 g (0.004 mol) of cobalt naphthenate as metal salt catalyst and 10.1 g (0.1 mol) of triethylamine as basic catalyst.
After adding , the reaction was carried out at 60° C. for 1 hour. After the reaction was completed, the reaction solution was cooled to 20° C., and 500 g of water was added to the reaction solution to precipitate a precipitate. This precipitate was filtered, washed with water, and then neutralized by adding an aqueous solution of sodium carbonate. After neutralization, 163g of N, N' was washed with water and dried.
-4,4'-diphenylmethane-bis-maleimide (pale yellow powder, yield 91%) was obtained.

Further, the purity of this compound was measured by liquid chromatography and was found to be 91.5%.

Example 4 143 g (0.4 mol) of N,N'-4,4'-diphenylmethane-bis-maleimide obtained in Example 1 was mixed with N,
Dissolved in 107 g of N-dimethylacetamide, and further added 39.6 g of diaminodiphenylmethane to make 80
The reaction was carried out at ℃ for 2 hours. A glass cloth was impregnated with the obtained varnish and then dried at 150° C. for 5 minutes to produce a prepreg.

The amount of resin impregnated in this prepreg was 50% of the total weight. Four sheets of this prepreg were stacked together, and then copper foil was stacked on both sides of the prepreg, at a temperature of 140°C for 6 hours.
Molding was carried out for 0 minutes at a pressure of 40 kgf/cd, and further,
Curing was performed at 230° C. for 2 hours to obtain a double-sided copper foil-clad laminate.

Example 5 In Example 4, N obtained in Example 1, N4.4
’-diphenylmethane-bis-maleimide instead of
A laminate was produced in the same manner as in Example 4, except that N,N'-44'-diphenylmethane-bis-maleimide obtained in Example 2 was used.

Comparative Example 2 In Example 4, N obtained in Example 1, N4.4
’-diphenylmethane-bis-maleimide instead of
A laminate was produced in the same manner as in Example 4, except that N,N'-44'-diphenylmethane-bis-maleimide obtained in Comparative Example 1 was used.

The Tg of the laminates obtained in Example 4, Example 5, and Comparative Example 2 was measured by TMA analysis. Furthermore, the adhesive strength between the eyebrows (between the prepregs) of each of these laminates was measured. The results are shown in Table 1 As shown in Table 1, the laminates obtained in Examples 4 and 5 had almost the same performance as the laminates obtained in Comparative Example 2. I understand.

〔Effect of the invention〕

In the method for producing an unsaturated dicarboxylic acid imide compound according to the present invention, an unsaturated dicarboxylic acid imide compound is reacted in the presence of an acid anhydride as a dehydrating agent, a basic catalyst, and a metal salt catalyst. Dehydration ring closure reaction of acid amidic acid compounds can be carried out at low temperature and in a short time. Therefore, according to this manufacturing method, there are extremely few high molecular weight components,
Moreover, a highly pure unsaturated dicarboxylic acid imide compound can be obtained. Furthermore, in this production method, after the completion of the ring-closing reaction, the by-produced acid is decomposed into alcohol and ester by orthoester and removed, so complicated purification steps such as neutralization of the acid are not necessary. Unsaturated dicarboxylic acid imide compounds can be obtained at low cost and in high yield.

Claims (1)

[Claims] 1 The following general formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・(I
) In the formula, D represents a divalent organic group having at least one carbon-carbon double bond, R^1 represents an n-valent organic group containing at least one carbon atom, and n is one or more Represents an integer. After dehydrating and ring-closing the unsaturated dicarboxylic acid amidic acid compound represented by in the presence of an acid anhydride as a dehydrating agent, a basic catalyst, and a metal salt catalyst, the by-produced acid is expressed by the following general formula (
II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼... (II) In the formula, R^2 and R^3 represent the same or different monovalent organic groups containing at least one carbon atom. By decomposing and removing alcohol and ester with the orthoester represented by A method for producing an unsaturated dicarboxylic acid imide type compound to obtain a type compound.