JPH085856B2 - Process for producing unsaturated dicarboxylic acid imide compound - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing an unsaturated dicarboxylic acid imide compound used for producing an addition type imide resin used for printed wiring boards and the like.

[0002]

2. Description of the Related Art One of the methods for producing an unsaturated dicarboxylic acid imide compound is a method of ring-closing an unsaturated dicarboxylic acid amide compound. One of the ring closure methods is, for example, the chemical ring closure method described in JP-A-53-23396. This chemical ring closure method is a method of performing dehydration ring closure using a dehydrating agent such as acetic anhydride. In this way, low temperature,
Since the reaction can be carried out in a short time, the obtained unsaturated dicarboxylic acid imide compound has a high purity of about 95% by weight, and the amount of the polymer component contained in the compound is small.

[0003]

However, in the case of the above-mentioned chemical ring closure method, usually, after completion of the reaction, water is added to the reaction solution to precipitate the reaction product, and filtration, water treatment, and by-product are carried out. Neutralize the acid. These post-treatment steps are very complicated, time-consuming and costly. Further, there is a problem that the purity decreases during these post-treatment steps.

The present invention has been made in view of the above circumstances, and does not require a complicated post-processing step and can be performed in a short time.
An object of the present invention is to provide a method capable of obtaining a highly pure unsaturated dicarboxylic acid imide compound at low cost.

[0005]

In order to solve the above problems, a method for producing an unsaturated dicarboxylic acid imide compound according to the present invention is to dehydrate an unsaturated dicarboxylic acid amic acid compound represented by the following general formula (3). After dehydration and ring closure in the presence of acid anhydride, basic catalyst and metal salt catalyst as agents, the resulting reaction product solution is sprayed to give an unsaturated dicarboxylic acid represented by the following general formula (4). It is intended to obtain an acid imide compound.

[0006]

[Chemical 3]

[0007]

[Chemical 4]

[In the formulas 3 and 4, D is at least 1
Represents a divalent organic group having one carbon-carbon double bond, R
¹ represents an n-valent organic group containing at least one carbon atom, and n represents an integer of 1 or more. The present invention will be described in detail below. The method for obtaining the unsaturated dicarboxylic acid amic acid compound represented by the general formula 3 used in the present invention is not particularly limited, but for example, the unsaturated dicarboxylic acid represented by the following general formula 5 is used. Obtained by reacting an anhydride with an amine or polyamine represented by the following general formula 6, preferably in the presence of an organic solvent inert to the reaction system or in a solventless system. You can

[0009]

[Chemical 5]

[0010]

[Chemical 6]

[In formulas 5 and 6, D is at least 1
Represents a divalent organic group having one carbon-carbon double bond, R
¹ represents an n-valent organic group containing at least one carbon atom, and n represents an integer of 1 or more. The unsaturated dicarboxylic acid anhydride that can be used in this reaction system is not particularly limited, but examples thereof include the following compounds.

Maleic anhydride, citraconic anhydride, itaconic anhydride, tetrahydrophthalic anhydride, nadic acid anhydride, and their halogen-substituted compounds, alkyl-substituted compounds and the like. These compounds may be used alone or in combination of two or more. Examples of amines or polyamines include, but are not limited to, the following compounds. The following compounds also alone
Alternatively, a plurality of types can be used together.

Methylamine, ethylamine, 1-propylamine, 1,2-dimethylpropylamine, 3-methoxypropylamine, 3-ethoxypropylamine, 3
-Propoxypropylamine, 3-isopropoxypropylamine, 3-butoxypropylamine, 3-isobutoxypropylamine, 3- (2-ethylhexyloxy) propylamine, 3-laurioxypropylamine, 3-myristyloxypropylamine, Methylaminopropylamine, dimethylaminopropylamine, diethylaminopropylamine, dibutylaminopropylamine, 2-hydroxyethylaminopropylamine,
Dimethylaminoethoxypropylamine, laurylaminopropylamine, diethanolaminopropylamine, iminobispropylamine, methylaminobispropylamine, n-butylamine, isobutylamine, se
c-Butylamine, hexylamine, 2-ethylhexylamine, dodecylamine, cyclohexylamine, arylamine, 3-decycloxyamine, dimethylaminoethylamine, diethylaminoethylamine, ethylaminoethylamine, α-phenethylamine, β-phenethylamine, fafurylamine , Methoxyamine, m-
Aminobenzylamine, metaphenylenediamine, 4-
Chlormetaphenylenediamine, 5-nitrometaphenylenediamine, 4,6-dimethylmetaphenylenediamine, paraphenylenediamine, 2-chloroparaphenylenediamine, 2-nitroparaphenylenediamine, 2-
Cyanoparaphenylenediamine, 2,5-dichloroparaphenylenediamine, 2,6-dichloroparaphenylenediamine, 2,5-diethylparaphenylenediamine,
5-chloro-2-methylparaphenylenediamine, tetrafluorophenylenediamine, tolylenediamine,
3,5-diethyl-2,4-tolylenediamine, 2-picolylamine, 3-picolylamine, 4-picolylamine, metaxylylenediamine, paraxylylenediamine, hexamethylenediamine, heptamethylenediamine, 4,4 -Dimethylheptamethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaacetylenehexamine, 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'-dimethylphenylmethane, 4,4'-bis (p-
Aminophenoxy) diphenylmethane, 4,4′-bis (m-aminophenoxy) diphenylmethane, 2,2 ′
3,3'-tetrachloro-4,4'-diaminodiphenylmethane, diaminodicyclohexylmethane, 4,4 '
-Bis (p-aminophenoxy) diphenylmethane,
4,4'-bis (m-aminophenoxy) diphenylethane, 1,2-bis- (3-aminopropoxy) -ethane, 2-aminopropanol, 3-aminopropanol, 1,2-diaminopropane, 1,3 -Diaminopropane, 4,4'-diaminodiphenylpropane, 3,
3'-diaminodiphenylpropane, 1,2-bis-
(3-Aminopropoxy) -2,2-dimethylpropane, 4,4'-bis (p-aminophenoxy) diphenylpropane, 4,4'-bis (m-aminophenoxy) diphenylpropane, 2,2-bis ( 4-aminophenyl) propane, 1,4-diaminobutane, 1,4-
Diaminocyclohexane, bis- (3-aminopropyl) ether, α, ω-bis- (3-aminopropyl)
-Polyethylene glycol ether, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether,
3,4,4'-triaminodiphenyl ether, 3,
3 ', 4,4'-tetraaminodiphenyl ether, bis (p-βamino-tertbutylphenyl) ether, toluidine, 4,4'-methylenedi-o-toluidine,
4,4'-methylenedi-6-bromo-2-toluidine,
Aniline, ethylaniline, dichloroaniline, 4,
4'-methylenedi-2,6-diethylaniline, 4,
4'-methylenedi-2,6-isopropylaniline, isopropoxyaniline, chloroaniline, bromoaniline, iodoaniline, nitroaniline, 4,4'-methylenedi-2,6-dibromoaniline, 4,4'-methylenedi- 2-bromo-6-chloroaniline, bis-p-aminophenylaniline, methylenebisanthraanilic acid, methylenebismethylanthranilate,
3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 3,3 ', 4,4'-tetraaminodiphenyl sulfone, p-bis (4-aminophenoxy) diphenyl sulfone, p-bis (3 -Aminophenoxy) diphenyl sulfone, 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, 1-amino-4-methylpiperazine, 1,
4-bisaminopropylpiperazine, N-aminopropylpiperazine, 1-amino-4-cyclohexylpiperazine, 2-aminopyrazine, 2-aminopyridine, 3-
Aminopyridine, 4-aminopyridine, 2,3-diaminopyridine, 2,5-diaminopyridine, 2,6-diaminopyridine, 2,3,6-triaminopyridine, 2-
Amino-3-methylpyridine, 2-amino-4-methylpyridine, 2-amino-5-methylpyridine, 2-amino-6-methylpyridine, 2-amino-4-ethylpyridine, 2-amino-4-propyl Pyridine, 2-amino-4,6-dimethylpyridine, 2,6-diamino-4-
Methylpyridine, 2-amino-3-nitropyridine, 2
-Amino-5-nitropyridine, 2-chloro-4-aminopyridine, 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-triazine, p-bis (4-aminophenoxy) benzene, m
-Bis (4-aminophenoxy) benzene, p-bis (3-aminophenoxy) benzene, m-bis (3-aminophenoxy) benzene, 1,3,5-triaminobenzene, 4,4'-diamino-3 -Methoxyazobenzene, 1,5-diaminonaphthalene, 1,3,5-triaminonaphthalene, 3,3'-dimethyl-4,4'-diaminobiphenyl, 4,4'-diaminooctafluorobiphenyl, 2,5- Diaminoterephthalic acid, 3,4'-
Diaminobenzanilide, 4,4'-diaminobenzanilide, 4- (p-aminophenoxy) -4-aminobenzanilide, 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 (βamino-tertbutyl) toluene, 4,4′-diaminobenzophenone, polytetramethylene oxide-di-p-aminobenzoate, Trimethylene bis- (4-aminobenzoate), 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-hydroanthracene, 2,6-
Diaminoanthraquinone, 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'-methylenedi-2,6-xylidine, 2,6-diaminobenzothiazole, m-aminobenzoic acid hydrazide,
2,4-diaminomesitylene, hexaaminocyclophosphazene, 1,1-diamino-3,3,5,5-tetraphenoxycyclophosphazene, 1,3,5-tris (p-aminophenoxy) -1 , 3,5-triphenoxycyclophosphazene, hexakis (p-aminophenoxy) -cyclophosphazene and the like.

The acid anhydride, which is a dehydrating agent for dehydrating and ring-closing the unsaturated dicarboxylic acid amide compound represented by the general formula 3, is not particularly limited. Can be mentioned. Lower monoalkylcarboxylic acid anhydrides such as acetic anhydride, propionic anhydride and butyric anhydride.

The amount of the dehydrating agent used is not particularly limited, but for example, the amount of the dehydrating agent is preferably 1 to 5 mol, more preferably 1.2 to 3 mol, per equivalent of the amic acid group. The basic catalyst used in the dehydration ring closure is not particularly limited, but examples thereof include the following compounds.

Trialkylamines having an alkyl group having 1 to 10 carbon atoms such as trimethylamine, triethylamine and tri-n-butylamine, N, N-dimethylbenzylamine, N-methylmorpholine, 1,8-diazabicyclo [5,5]. 4,0] 7-undecene and the like. The amount of the basic catalyst used is not particularly limited, but for example,
Basic catalyst 0.001 to 0.5 per equivalent of amic acid group
A molar range is preferred.

The metal salt catalyst used in the dehydration ring closure is not particularly limited, but examples thereof include the following compounds. Divalent or trivalent cobalt compounds such as cobalt chloride, cobalt carbonate, cobalt sulfate and cobalt naphthenate, nickel acetate, nickel (acetylacetonate), divalent nickel compounds such as nickel carbonate, magnesium chloride, magnesium carbonate, acetic acid magnesium,
Divalent magnesium compounds such as magnesium perchlorate,
Monovalent sodium compounds such as sodium acetate.

The amount of the metal salt catalyst used is not particularly limited. For example, unsaturated dicarboxylic acid amic acid is used.
The range of 0.0001 to 0.2 times the weight of the compound is preferable. In this reaction system, an organic solvent is usually used. The organic solvent that can be used is not particularly limited, but examples thereof include the following organic solvents. Dimethylformamide, dimethylacetamide, dimethylsulfoxide, N
-Methylpyrrolidone, acetonitrile, acetone, dioxane, benzene, toluene, xylene, cyclohexane, methyl ethyl ketone, methyl isobutyl ketone, tetrahydrofuran and the like. Each of these organic solvents is
They can be used alone or in combination of two or more.

The amount of the organic solvent used is not particularly limited, but is preferably about 1.0 to 4.0 times the weight of the unsaturated dicarboxylic acid amide compound. The dehydration ring closure reaction is preferably carried out at a temperature of 20 to 100 ° C., although not particularly limited. More preferably, it is 40 to 80 ° C.

After carrying out the dehydration ring closure reaction in this manner,
The obtained reaction product liquid contains the solvent used in the reaction and an alkylcarboxylic acid as a by-product, in addition to the unsaturated dicarboxylic acid imide compound represented by the general formula 4 which is the target product. Has been. Therefore, in the present invention, the reaction product solution is sprayed to distill off the alkylcarboxylic acid, the solvent and the like to obtain a highly pure unsaturated dicarboxylic acid imide compound.

The method of spraying the reaction product liquid is not particularly limited, but in order to enhance the efficiency of distilling off the solvent and the like, spraying is carried out under any of the following conditions (a) to (c). It is preferable to carry out. (A) Under heating conditions. (B) Under reduced pressure conditions.

(C) Under heating and reduced pressure conditions. When spraying under the conditions (a) or (c), the heating temperature is preferably 180 ° C. or lower. 180 ° C
At more than temperature, because the self-polymerization is likely to occur in the unsaturated dicarboxylic acid imide compound, a reduction in the purity of the unsaturated dicarboxylic acid imide compound obtained is invited Cucamonga et al.

[0023]

When the unsaturated dicarboxylic acid amic acid compound is dehydrated and ring-closed in the presence of an acid anhydride, a basic catalyst and a metal salt catalyst, the resulting reaction product solution is sprayed to produce this reaction. Since the solvent contained in the product solution and the alkylcarboxylic acid as a by-product are easily distilled off by spraying, a highly pure unsaturated dicarboxylic acid can be obtained in a short time at low cost without requiring a complicated post-treatment step. It is possible to obtain an acid imide compound.

[0024]

EXAMPLES Next, examples of the present invention will be described together with comparative examples, but the present invention is not limited to the following examples. -Example 1-Unsaturated dicarboxylic acid amic acid having the structure of the following formula 7:

[0025]

[Chemical 7]

(Compound name: N, N'-4,4'-diphenylmethane bismaleamic acid) 197 g (0.5 mol)
Was dissolved in 394 g of N, N′-dimethylformamide, and 153.0 g (1.5 mol) of acetic anhydride, 5.1 g (0.05 mol) of triethylamine, and 0.2 g (0.001 mol) of nickel acetate were added. After adding, the reaction was carried out for 30 minutes while maintaining the reaction temperature at 65 ° C.

After completion of the reaction, spraying of the reaction product liquid was carried out by a spray dryer (Kuraksu system manufactured by Hosokawa Micron Co., Ltd.) under the conditions of heating temperature of 180 ° C. and vacuum degree of 10 Torr. Was obtained. The time required for spraying at this time was about 5 minutes. When the structure of the obtained solid compound was confirmed by ¹³ C-NMR, it was confirmed that the compound was an unsaturated dicarboxylic acid imide compound (compound name: N, N'-
4,4'-diphenylmethane bismaleimide).

[0028]

Embedded image

The purity of this compound measured by liquid chromatography was 95.5%. This N,
N'-4,4'-diphenylmethane bismaleimide 10
0 g was taken out and put into another reaction container, and N,
After adding and dissolving 75 g of N'-dimethylacetamide, 27.7 g of diaminodiphenylmethane was added,
The reaction was carried out at 0 ° C for 2 hours to obtain a varnish.

A glass cloth was impregnated with the obtained varnish and then dried at 150 ° C. for 5 minutes to prepare a prepreg. Four of these prepregs were superposed, copper foils were superposed on both sides of the prepreg, and molding was performed at a temperature of 140 ° C. for a time of 60 minutes at a pressure of 40 kgf / cm ² , and further 2
Curing was performed at 30 ° C. for 2 hours to obtain a double-sided copper-clad laminate.

The Tg of this laminate was measured by TMA analysis and found to be 250 ° C. The adhesive strength between the layers (between the prepregs) was measured and found to be 1.3 kg.
It was f / cm. -Example 2-N, N'-4,4'-diphenylmethane bismaleamic acid 197 g (0.5 mol) of methyl ethyl ketone 500
12 g of acetic anhydride (1.25
Mol), 10.1 g (0.1 mol) of N-methylmorpholine, and 0.2 g (0.001 mol) of cobalt acetate were added, and then the mixture was reacted for 3 hours while maintaining the reaction temperature at 60 ° C.

After completion of the reaction, the spraying of the reaction product liquid was carried out by using the same apparatus as in Example 1 so that the heating temperature was 16
When performed at 0 ° C. and a vacuum degree of 40 Torr, a yellow solid compound was obtained. The time required for spraying at this time was about 5 minutes. When the structure of the obtained solid compound was confirmed by ¹³ C-NMR, the compound was found to be the unsaturated dicarboxylic acid imide compound obtained in Example 1 (compound name: N, N′-4,4′-diphenylmethane). Bismaleimide).

The purity of this compound measured by liquid chromatography was 93.3%. -Example 3-Unsaturated dicarboxylic acid amic acid having the structure of the following formula 9:

[0034]

[Chemical 9]

(Compound name: N-phenylmaleamic acid)
191 g (1 mol) was dissolved in 287 g of methyl ethyl ketone, and 127.5 g (1.25 mol) of acetic anhydride, 10.1 g (0.1 mol) of triethylamine, and 0.2 g (0.001 mol) of cobalt naphthenate were dissolved therein. After the addition, the reaction was carried out for 60 minutes while maintaining the reaction temperature at 60 ° C. After the completion of the reaction, spraying of the reaction product liquid was performed under the conditions of a heating temperature of 140 ° C. and a vacuum degree of 7 Torr by using the same apparatus as in Example 1. As a result, a yellow solid compound was obtained. The time required for spraying at this time was about 5
It was about a minute.

The structure of the obtained solid compound was analyzed by ¹³ C-NMR.
As a result, it was confirmed that the compound was an unsaturated dicarboxylic acid imide compound (compound name: N
-Phenylmaleimide).

[0037]

[Chemical 10]

The purity of this compound measured by liquid chromatography was 92.1%. -Example 4-Unsaturated dicarboxylic acid amic acid having the structure of formula 11 below:

[0039]

[Chemical 11]

(Compound name: N, N'-4,4'-diphenyl ether bismaleamic acid) 198 g (0.5 mol) was dissolved in N, N'-dimethylformamide 396 g, and acetic anhydride 153 g (1 0.5 mol), 5.1 g (0.05 mol) of triethylamine and 0.2 g (0.001 mol) of cobalt acetate were added, and then the reaction was carried out for 60 minutes while maintaining the reaction temperature at 70 ° C.

After completion of the reaction, the spraying of the reaction product liquid was carried out by using the same apparatus as in Example 1, and the heating temperature was 18
When performed at 0 ° C. and a vacuum degree of 10 Torr, a yellow solid compound was obtained. The time required for spraying at this time was about 5 minutes. The structure of the obtained solid compound was confirmed by ¹³ C-NMR. As a result, it was confirmed that the compound was an unsaturated dicarboxylic acid imide compound (compound name: N, N'-4,4'- Diphenyl ether bismaleimide).

[0042]

[Chemical 12]

The purity of this compound measured by liquid chromatography was 94.1%. -Comparative Example- 197 g (0.5 mol) of N, N'-4,4'-diphenylmethane bismaleamic acid was dissolved in 394 g of N, N'-dimethylformamide, and acetic anhydride 127.5 was added thereto.
g (1.25 mol), triethylamine 5.1 g (0.
05 mol), nickel acetate 0.2 g (0.001 mol)
After adding, the reaction was carried out for 30 minutes while maintaining the reaction temperature at 65 ° C.

After completion of the reaction, the reaction solution was cooled to 20 ° C. and 500 g of water was added to the reaction solution to deposit a precipitate. The precipitate is filtered off, washed with water, then neutralized with an aqueous solution of sodium carbonate,
After completion of neutralization, by further washing with water and drying,
A solid of N, N'-4,4'-diphenylmethane bismaleimide was obtained. The time required for washing, neutralization, and drying at this time was about 5 hours. Also, at this time, about 300
0 g of waste solution came out.

The purity of the obtained imide compound was measured by liquid chromatography and found to be 90.5%, which was lower than that of the examples.

[0046]

EFFECTS OF THE INVENTION According to the method for producing an unsaturated dicarboxylic acid imide compound according to the present invention, unlike the conventional method, it is not necessary to carry out complicated post-treatment steps such as neutralization and washing with water, and it is very convenient to use the spray method. Since the post-treatment step is performed by a simple method, a highly pure unsaturated dicarboxylic acid imide compound can be obtained in a short time and at low cost.

Front page continuation (72) Inventor Hidetaka Kakiuchi 1048 Kadoma, Kadoma City, Osaka Prefecture Matsushita Electric Works Co., Ltd. (56) References JP 53-23396 (JP, A) JP 63-69827 (JP, JP, 69,827) A) US Patent 4855450 (US, A)

Claims (3)

[Claims] 1. An unsaturated dicarboxylic acid amic acid compound represented by the following general formula 1 is dehydrated and ring-closed in the presence of an acid anhydride as a dehydrating agent, a basic catalyst and a metal salt catalyst. A process for producing an unsaturated dicarboxylic acid imide compound, which comprises spraying the obtained reaction product liquid to obtain an unsaturated dicarboxylic acid imide compound represented by the following general formula 2. Embedded image Embedded image [In Formulas 1 and 2, 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 Represents an integer of 1 or more. ] 2. The method for producing an unsaturated dicarboxylic acid imide compound according to claim 1, wherein the spraying of the reaction product liquid is carried out at a heating temperature of 180 ° C. or lower. 3. The method for producing an unsaturated dicarboxylic acid imide compound according to claim 1, wherein the reaction product solution is sprayed under reduced pressure.