JPS63174967A - Production of unsaturated dicarboximide based compound - Google Patents

Abstract

PURPOSE:To obtain the titled compound useful for producing addition type imide resins, etc., in high purity at a low cost without using a dehydrating agent, by reacting an unsaturated dicarboxylic acid anhydride with a compound capable of forming an isocyanate compound at a reaction temperature. CONSTITUTION:A compound expressed by formula I (D is bifunctional organic group having >=1 carbon-carbon double bonds) is reacted with at least one of compounds expressed by formulas II and III (R1 is >=1C monofunctional organic group; R2 is >=1C n-functional organic group) in or without an organic solvent preferably at 20-200 deg.C, particularly 50-150 deg.C temperature to afford the aimed compound expressed by formula IV. According to this method, production cost can be reduced since a dehydration step is not required. Side reaction of an isocyanate compound can be suppressed because of no direct use thereof for the reaction. Thereby the above-mentioned effects are obtained. Furthermore, the compounds expressed by formulas II and III are obtained by, e.g. reacting a compound expressed by formula V with a compound expressed by the formula R1-H or R1-OH.

Description

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

[Background technology]

When producing unsaturated dicarboxylic acid imide compounds used in the production of addition-type imide resins, conventionally, a carboxylic acid anhydride such as maleic anhydride is reacted with a compound having an amino group, and then this is dehydrated. A method of dehydration and ring closure using a chemical agent, etc. has been carried out.

However, in this method, as mentioned above, a dehydrating agent etc. must be used, and the produced acetic acid etc. must be separated from the target product, resulting in high production costs.
This is one of the reasons why unsaturated dicarboxylic acid imide compounds are expensive.

On the other hand, it is generally known that the unsaturated dicarboxylic imide compound can be obtained by reacting a carboxylic acid anhydride with an isocyanate compound.

Since this method does not use a dehydrating agent or the like, it is possible to reduce costs.

However, since the isocyanate compounds used in this method are extremely reactive, they cause side reactions such as polymerization, making it impossible to obtain highly pure unsaturated dicarboxylic acid imide compounds. be.

[Purpose of the invention]

The present invention was made in view of the above circumstances, and an object of the present invention is to provide a method for producing a highly pure unsaturated dicarboxylic acid imide compound at a low cost.

Disclosure of the Invention] To achieve the above object, the present invention provides an unsaturated dicarboxylic acid anhydride represented by the following general formula (1), a compound represented by the following general formula (n), and , an unsaturated dicarboxylic acid imide compound obtained by reacting with at least one of the compounds expressed by the following general formula (TV) to obtain an unsaturated dicarboxylic acid imide compound expressed by the following general formula (TV) The gist is the manufacturing method.

The present invention will be explained in detail below.

The unsaturated dicarboxylic anhydride used in this invention is
It refers to a compound represented by the following general formula (I). However, in the formula, a divalent organic group having at least one carbon-carbon bond is included.

Examples of the unsaturated dicarboxylic anhydride represented by the above formula (1) include, but are not limited to, the following compounds.

maleic anhydride, citraconic anhydride, itaconic anhydride,
Tetrahydrophthalic anhydride, nadic anhydride, and their halogen-substituted products, alkyl-substituted products, etc.

In this invention, the above-mentioned unsaturated dicarboxylic acid anhydrides can be used alone or in combination.

The compound that reacts with the unsaturated dicarboxylic anhydride as described above is at least one of the following general formula (U) and the following general formula (III).

However, in the above formulas (n) and (III), R1 represents a monovalent organic group containing at least one carbon atom,
R2 represents an n-valent organic group containing at least one carbon atom.

The above compounds (n) or (III) can be used alone or in combination with (II) and (III). In addition, compounds (n) and (III)
Even in the case of only one, it is also possible to use a plurality of compounds having different R and R2 together.

The compounds of the above formulas (n) and (III) are, for example, an isocyanate compound of the following general formula (IV) (0=C=N+TRt...(IV)) and a compound of the general formula H-R , or HO-R, preferably in the presence of an organic solvent inert to the reaction system or in a solvent-free system. It is believed that the compound (II), (I[I) reacts with the unsaturated dicarboxylic acid anhydride represented by the formula (1) as follows. That is, these compounds (II), (III ) generally dissociates into the isocyanate compound of formula (IV) and H-R or HO-R1 when heated to a predetermined temperature. It is thought that an unsaturated dicarboxylic acid imide compound is obtained by reacting with an unsaturated dicarboxylic acid.

The types of the compounds (n) and (III) are not particularly limited in the present invention, but the following are preferred as the isocyanate compounds that serve as raw materials.

Methane diisocyanate, butane-1,1-diisocyanate, ethane-1,2-diisocyanate, butane-
1,2-diisocyanate, transvinylene diisocyanate, propane-1°3-diisocyanate, butane-1,4-diisocyanate, 2-butene-1,4-
Diisocyanate, 2-methylbutane-1,4-diisocyanate, pentane-1,5-diisocyanate, hexane-1,6-diisocyanate, heptane-1,7
-diisocyanate, octane-1,8-diisocyanate, nonane-1,9-diisocyanate, decane-1
, 10-diisocyanate, dimethylsilane diisocyanate, diphenylsilane diisocyanate, Q, ω'
-1,3-dimethylbenzenediisocyanate, ω, ω
'-1゜4-dimethylbenzene diisocyanate, ω,
ω'-1.3-dimethylcyclohexane diisocyanate, ω, ω'-1.4-dimethylcyclohexane diisocyanate, ω, ω'-1.4-dimethylnaphthalene diisocyanate, ω, ω'-1.5-dimethylnaphthalene diisocyanate, Cyclohexane-1,3-diisocyanate, cyclohexane-1,4-diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, 1,3-phenylene diisocyanate, 1.4-
Phenyl diisocyanate, 1-methylbenzene-2
, 4-diisocyanate, ■-methylbenzene-2,5
-diisocyanate, -Methylbenzene-2,6-diisocyanate, 1-methylbenzene-3,5-diisocyanate, diphenyl ether-4,4'-diisocyanate, diphenyl ether-2,4'-diisocyanate, naphthalene-1,4-diisocyanate, naphthalene -1,5-diisocyanate, biphenyl-4゜4'-diisocyanate, 3,3'-dimethylbiphenyl-4,4'-diisocyanate, 2,3'-dimethoxybiphenyl-4,4'-diisocyanate, diphenylmethane-4, 4'-diisocyanate, 3.3'-dimethoxydiphenylmethane-4,4'-diisocyanate, 4.4'-dimethoxydiphenylmethane-3,3'
-Diisocyanate, diphenyl sulfide-4,4
'-diisocyanate, diphenylsulfone-4,4'
- bifunctional isocyanate compounds such as diisocyanate, polymethylene polyphenylisocyanate, triphenylmethane triisocyanate, tris(4-phenylisocyanate thiophosphate), 3.3',
4. Trifunctional or higher functional isocyanate compounds such as 4'-diphenylmethanetetrisocyanate, dimers or trifunctional compounds of the above isocyanate compounds, etc.

In this invention, the above isocyanate compound alone,
Alternatively, a plurality of them can be used together.

Examples of compounds represented by the general formula HO-R or HR include the following, but compounds other than these may also be used.

methanol, ethanol, propatool, butanol,
Ethylene glycol, methyl cellosolve, methyl calpitol, benzyl alcohol, cyclohexanol, phenol, cresol, xylenol, p-tert-
Butylphenol, p-chlorophenol, p-naphthol, p-nitrophenol, dimethyl malonate, ethyl acetoacetate, butylmercaptan, thiophenol,
Acetanilide, acetamide, acrylamide, henzamide, succinimide, diphenylamine, phenylnaphthylamine, aniline, imidazole, urea, thiourea, phenyl N-phenylcarbamate, 2-oxazolidone, ethyleneimine, formaldoxime, acetaldoxime, methyl ethyl keto Oxime, cyclohexanone oxime, etc.

The above compounds can be used alone or in combination.

As the organic solvent inert to the reaction system used when reacting the above isocyanate compound with HO-R1 or HR, the following are preferred.

Acetone, dioxane, chloroform, benzene, toluene, xylene, hexane, cyclohexane, methyl ethyl ketone, methyl isobutyl ketone, ether, tetrahydrofuran, dimethylacetamide, N-methyl-
2-pyrrolidone, dimethylformamide, dimethylcarpitol.

In this invention, as a method for obtaining the compounds of formulas (■) and (III), the above isocyanate compound and HO-
In addition to the method of reacting R or H--R, for example, the following method may be used. However, in consideration of cost, ease of reaction, etc., it is preferable to perform a method of reacting the isocyanate compound with HO-R1 or HR+.

(2) A method of reacting a compound represented by the following general formula (V) with HO-R or H-R7.

(2) A method of reacting a compound represented by the general formula (Ht N+TRt) with a compound represented by the following general formula (Vl) or (■).

HO-C-R.

II...(Vl) ■ A compound with the general formula (H, N←nR2,
A method of reacting with a compound represented by the following general formula (■) or (IX).

A compound of formula (n) or (III) as described above and an unsaturated dicarboxylic acid anhydride of formula (1),
When heated in an organic solvent or without a solvent, compound (n) or (II
I) dissociates to form an isocyanate compound and HO-R1
or H-R. Then, the produced isocyanate compound and the unsaturated dicarboxylic anhydride react to obtain an unsaturated dicarboxylic imide compound represented by the formula -a (TV). At this time, the compound (n) or (II[)
are much more thermally stable than isocyanate compounds, and there is no risk of side reaction products being produced. Moreover, since the isocyanate compound generated by heating immediately reacts with the unsaturated dicarboxylic anhydride, there is no fear that this isocyanate compound will cause side reactions such as polymerization. Therefore, according to the method for producing an unsaturated dicarboxylic acid imide compound of the present invention, it is possible to obtain an unsaturated dicarboxylic acid imide compound of very high purity at low cost because it does not require a dehydration step unlike the conventional method. It becomes possible to do this.

The conditions for the above reaction are an isocyanate compound or HO-R, which becomes a compound of formula (rl) or (m).

Although it varies depending on the type of HRt etc., the heating temperature is 20-20
The temperature is preferably 0°C, more preferably 50 to 150°C, and the heating time is preferably about 1 to 20 hours. Since the unsaturated dicarboxylic anhydride is required in an amount equal to or more than equimole to the isocyanate compound produced by the dissociation reaction, the unsaturated dicarboxylic anhydride must be blended with the compound of formula (■) or (III). The ratio is preferably about 1.0 to 2.0 in terms of molar ratio.

Examples of solvents that can be used in the reaction system for obtaining the compound of general formula (IV) include the above-mentioned isocyanate compound and HOR+ or HR.

The solvent used in the reaction with can be used as is, but other solvents may also be used.

When using each of the above-mentioned solvents, the above-mentioned isocyanate compound and HO-R,,H-
The reaction product with R1 was converted into the general formula (IV
) can also be used in the reaction to obtain the compound. Nao,
It goes without saying that the reaction product of the above-mentioned isocyanate compound and HO-R, H-R, may be used in the form of an isolated powder in the next reaction.

A catalyst can also be used for the reaction to obtain the compound of general formula (IV). Examples of catalysts that can be used include the following compounds, but it is of course possible to use other catalysts.

N-methylmorpholine, triethylamine, diazabicyclooctane, cobalt naphthenate, dibutyltin dilaurate, tin octylate, tributyltin acetate, dibutyltin diacetate.

Next, examples of the present invention will be described together with comparative examples.

(Example 1) 163 g (2.2 mol) of tert-butyl alcohol was used as the compound prepared by HO-R, and 250 g (1.0 mol) of diphenylmethane-4゜4'-diisocyanate was used as the isocyanate compound. Then, it was weighed into a flask along with 400 g of acetone as a solvent. Thereafter, a stirring rod, a thermometer, and a condenser were attached to the flask, and stirring and temperature raising were started.

When the liquid temperature reached 50 to 60°C, stirring was continued while maintaining this temperature, and a white solid began to precipitate. After about 3 hours (continued stirring), the reaction system was cooled to complete the reaction. After the reaction, the excess ter
When t-butyl alcohol and acetone were completely removed and the obtained reaction product was measured by CII-NMR, this compound was found to be a compound belonging to the general formula (n) expressed by the following formula. The purity was measured by liquid chromatography and was 99.0%.

194 g (0.5 mol) of the reactant obtained as described above and 108 g (1.1 mol) of maleic anhydride, which is an unsaturated dicarboxylic anhydride, were placed in a flask together with 300 g of dimethylacetamide, a solvent. After weighing, a push rod, thermometer and condenser were attached to the flask, and stirring and temperature raising were started. When the liquid temperature reached 120°C, bubbles appeared on the liquid surface. When these bubbles were collected and passed through a gas detection tube, a large amount of CO□ was detected. After continuing the reaction for about 2 hours until the generation of COz subsided, the reaction system was cooled and the reaction was terminated. After the reaction, the reaction solution was poured into water at 1000 mZ for dispersion, and the reaction product was deposited as a precipitate. The obtained precipitate was filtered, washed with water, and thoroughly dried to obtain a yellow powder. When this yellow powder was analyzed by C''-NMR, it was confirmed to be a maleic acid imide compound represented by the following general formula.

Further, the purity of this maleic acid imide compound was measured by liquid chromatography and was found to be 96.5%.

(Example 2) Phenol 20 as a compound treated with HO-R,
A maleic acid imide compound was obtained in the same manner as in Example 1 except that 7.0 g (2.2 mol) was used. The purity of the maleic acid imide compound obtained was measured by liquid chromatography and found to be 95.4%.

(Example 3) Compound 1 belonging to general formula (n) obtained in Example 1 above
94 g (0.5 mol) and 108 g (1 mol) of maleic anhydride.
, 1 mol) and the catalyst N-methylmorpholine 1.
94 g and 300 g of dimethylcarpitol as a solvent were weighed into a flask and reacted in the same manner as in Example 1 to obtain a maleic acid imide compound. The purity of the obtained maleic acid imide compound was measured by liquid chromatography and found to be 97.0%.

(Example 4) 194 g (0.5 mol) of the compound belonging to the general formula (II) obtained in Example 1 and 108 g (0.5 mol) of maleic anhydride (
(1.1 mol) was ground into powder in a mortar, and this powder was directly placed in a 60 x 60 cm tray and reacted without a solvent to obtain a maleic acid imide compound. The purity of the obtained maleic acid imide compound was measured by liquid chromatography and found to be 94.7%.

(Example 5) The compound belonging to the general formula (If) obtained in Example 1 was used as a solution, and 216 g of maleic anhydride (
Example 1 except that the reaction was carried out by adding 2.2 mol)
A maleic acid imide compound was obtained in the same manner as above. The purity of the obtained maleic acid imide compound was measured by liquid chromatography and found to be 96.3%.

(Example 6) Aniline 204.6 as a compound prepared by HRi
g (2.2 mol) and 250 g of diphenylmethane-4,4'-diisocyanate (2.2 mol) as an isocyanate compound.
1.0 mol) was used in each case, which was weighed into a flask together with 400 g of acetone as solvent. Thereafter, a stirring rod, a thermometer, and a condenser were attached to the flask, and stirring and temperature raising were started. Liquid temperature is 5
When the temperature reaches 0 to 60℃, while maintaining this temperature,
After stirring for about 3 hours, the reaction system was cooled to complete the reaction. After the reaction, excess aniline and acetone were completely removed, and the resulting reaction product was ”
-When measured by NMR, it was expressed by the following formula,
The purity of this compound belonging to the general formula (I[I) was measured by liquid chromatography and found to be 98.8%.

218 g (0.5 mol) of the reactant obtained as described above and 108 g (1.1 mol) of maleic anhydride, which is an unsaturated dicarboxylic anhydride, were placed in a flask together with 300 g of dimethylacetamide, a solvent. After weighing, a push rod, thermometer and condenser were attached to the flask, and stirring and temperature raising were started. When the liquid temperature reached 120°C, bubbles were observed on the liquid surface. When these bubbles were collected and passed through a gas detection tube, a large amount of COt was detected. After continuing the reaction for about 2 hours until the generation of Co2 subsided, the reaction system was cooled and the reaction was terminated. After the reaction, the reaction solution was poured into 1000 m of water and dispersed.
The reaction product was deposited as a precipitate. The obtained precipitate was filtered, washed with water, and thoroughly dried to obtain a powder. When this powder was analyzed with CICl5-N, it was confirmed to be a maleic acid imide compound expressed by the following general formula.

Further, the purity of this maleic acid imide compound was measured by liquid chromatography and was found to be 93.4%.

(Example 7) Acetamide 129 as a compound prepared by H-R
．． A maleic acid imide compound was obtained in the same manner as in Example 6, except that 8 g (2.2 mol) was used. The purity of the obtained maleic acid imide compound was measured by liquid chromatography and found to be 92.1%.

(Comparative Example 1) Diphenylmethane-4,4 which is an isocyanate compound
'-diisocyanate 250 g (1,0 mol) and dicarboxylic acid anhydride maleic anhydride 216 g (2,2
mole) and? Dimethylcarpitol 450 as a vehicle
A maleic acid imide compound was obtained in the same manner as in Example 1, except that the sample and g were weighed into the flask. The purity of the obtained maleic acid imide compound was measured by liquid chromatography and found to be 46.3%. This is considered to be because the diphenylmethane-4,4'-diisocyanate caused side reactions such as polymerization during the reaction.

(Comparative Example 2) A maleic acid imide compound was obtained in the same manner as in Example 1 except that 2.5 g of N-methylmorpholine as a catalyst was added. The purity of the obtained maleic acid imide compound was measured by liquid chromatography and was found to be 53.2%. From this result, it was found that when an isocyanate compound is used, side reactions cannot be suppressed even if a catalyst that promotes the reaction is added.

〔Effect of the invention〕

The method for producing an unsaturated dicarboxylic acid imide compound of the present invention is as described above, and does not require the use of a dehydrating agent (because the unsaturated dicarboxylic acid imide compound can be obtained,
Manufacturing costs can be reduced. Further, according to the present invention, since the isocyanate compound is not directly used in the reaction, side reactions can be eliminated, and as a result, highly pure unsaturated dicarboxylic acid imide compounds can be produced at low cost. is now possible.

Claims (1)

[Claims] (1) Represented by the following general formula (I) ▲Mathematical formulas, chemical formulas, tables, etc.▼(I) [In the formula, D represents a divalent organic group having at least one carbon-carbon double bond] The unsaturated dicarboxylic acid anhydride and the following general formula (II) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (II) and the following general formula (III) ▲ Numerical formulas, chemical formulas, There are tables, etc. ▼ (III) [In formulas II and III above, R_1 represents a monovalent organic group containing at least one carbon atom, and R_2 represents an n-valent organic group containing at least one carbon atom. ] React with at least one of the compounds represented by to obtain an unsaturated dicarboxylic acid imide compound represented by the following general formula (IV) ▲ Numerical formula, chemical formula, table, etc. ▼ (IV) A method for producing unsaturated dicarboxylic acid imide compounds.