JPH07108902B2 - Aromatic imide alkenyl ether - Google Patents

Description

The present invention relates to a novel aromatic imide alkenyl ether.

An imide structure has been conventionally known as a molecular structure having excellent heat resistance, but a compound having an imide group generally has a high melting point and a low solubility, which causes a problem that it is difficult to handle.

N, N ′ as an imide compound for solving this problem
-Bismaleimides and addition polymerization products thereof with diamines are known, but the former has the drawback that the cured product is brittle and the latter is inferior in long-term heat deterioration resistance.

Based on the above, the inventors of the present invention have diligently studied the development of a thermosetting resin excellent in workability, processability, and cured physical properties while making the most of the heat resistance of the imide group, and as a result, have an imide group in the molecule Further, they have found that a compound having a specific alkenyl ether group at the terminal is extremely effective for the above purpose, and completed the present invention.

That is, the present invention provides the following general formula (I): [In the formula, Ar ¹ represents a residue of benzene, Ar ² represents a residue of benzene, biphenyl or benzophenone,
X is -XHCO- or And R represents hydrogen or a lower alkyl group. ] The aromatic imide alkenyl ether shown by these is provided.

The aromatic imide alkenyl ether represented by the general formula (I) dehydrates, for example, an aromatic polycarboxylic acid anhydride having two carboxyl groups at least at adjacent positions and an aromatic monoamine having one hydroxyl group. By carrying out the reaction, a compound having two hydroxyl groups at the terminal and at least one cyclic imide group in the molecule is obtained, and this can be produced by alkenyl etherification.

The method for producing the aromatic imide alkenyl ether represented by the general formula (I) will be described in detail below.

The aromatic polycarboxylic acid having at least two adjacent carboxyl groups can be represented by the following general formula (II).

[In the formula, Y represents a carboxyl group or a halogenocarbonyl group, and Y'represents hydrogen or a carboxyl group. However, when Y'is a carboxyl group, Y is a carboxyl group. Ar ² represents a residue of benzene, biphenyl or benzophenone. ] The aromatic polycarboxylic acid represented by the general formula (II) is
One or more of them are used as an acid anhydride or a dianhydride. An anhydride of tricarboxylic acid such as trimellitic acid or a tricarboxylic anhydride halide, pyromellitic acid, 3,3 ′, 4,4′-benzophenone Tetracarboxylic acid,
3,3 ′, 4,4′-diphenyltetracarboxylic acid, 2,2 ′, 3,
Examples thereof include dianhydrides of tetracarboxylic acids such as 3'-diphenyltetracarboxylic acid.

The aromatic monoamine having one hydroxyl group can be represented by the following general formula (III).

_{^{HO-Ar 1 -NH 2 (III}} ) wherein, Ar ¹ represents a residue of benzene. Examples of such an aromatic monoamine (III) include o-aminophenol, m-aminophenol, p-aminophenol and the like, and one or more of these are used.

The compound obtained by the dehydration reaction of the aromatic polycarboxylic acid (II) and the aromatic monoamine (III) having a hydroxyl group can be represented by the following general formulas (A) and (B).

[In the formula, Ar ¹ and Ar ² have the above-mentioned meanings. The compound represented by the above (A) is obtained by imidizing the above tetracarboxylic dianhydride and an aromatic monoamine having a hydroxyl group at a molar ratio of 1/2. The compound represented by the above formula (B) can be obtained by amidating and imidizing the above-mentioned tricarboxylic acid anhydride or tricarboxylic anhydride halide and an aromatic amine having a hydroxyl group at a molar ratio of 1/2.

The alkenyl etherification can be performed by using the alkenyl halide represented by the general formula (IV) and dehalogenating in the presence of an alkali.

[In the formula, R represents hydrogen or a lower alkyl group, and Z represents a halogen atom. ] Such alkenyl halides (IV) include allyl chloride, allyl bromide, methallyl chloride,
Methallyl bromide and the like are exemplified, and one or more of these are used, and the amount used may be equivalent to or more than the hydroxyl group. Regarding alkali, sodium hydroxide, potassium hydroxide, lithium hydroxide, potassium carbonate, sodium carbonate, lithium carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate, sodium methoxide, potassium methoxide, potassium acetate, sodium acetate, sodium formate. , Calcium hydroxide, barium hydroxide, strontium hydroxide, trimethylamine, triethylamine and the like. These can be used alone or in combination of two or more, and the amount thereof is equivalent to or more than the hydroxyl group. If As the reaction solvent for dehalogenation, for example, a ketone system, an aromatic system, an alcohol system, an ether system, or the like can be used, but from the viewpoint of solubility, dimethyl sulfoxide, N-methylpyrrolidone, dimethylformamide, acetonitrile, dimethylacetamide, An aprotic polar solvent such as hexamethylphosphortriamide is preferable, and the reaction temperature is usually 20 to 120.
It can be carried out at a temperature of ° C, and if it is carried out in an atmosphere of an inert gas such as nitrogen, a product having a good hue can be obtained.

After the reaction is performed until the free hydroxyl group is substantially disappeared, the aromatic imide alkenyl ether of the present invention can be obtained by removing the by-product alkali salt.
Here, the case where a part of the alkenylphenol by-produced by the Claisen transition is included is also included in the present invention.

The aromatic imide alkenyl ether thus obtained has a low melting point, has high solubility and is easy to handle, and is homopolymerized or copolymerized with other double bond-containing compounds, particularly maleimide compounds such as N, N'-bismaleimide. By doing so, it is useful as a heat-resistant thermosetting resin having excellent workability, processability, and cured physical properties. It is also useful as an intermediate when epoxidizing with hydrogen peroxide or the like.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.

Example 1 (Synthesis of terminal hydroxyl group-containing imide compound) In a 300 ml four-necked flask equipped with a thermometer, a condenser, and a stirrer, 18.0 g (0.165 mol) of m-aminophenol,
Charge 8.34 g (0.0825 mol) of triethylamine and 120 g of dimethylacetamide and raise the temperature to 50 ° C. 15.8 g (0.075 mol) of trimellitic anhydride chloride was dissolved in 31.6 g of dimethylacetamide in advance, and this solution was added dropwise while maintaining the temperature at 50 ° C. After the addition, the temperature was kept at the same temperature for 3 hours. After being kept warm, the mixture is cooled and the produced salt is removed by filtration.

After filtration, the resin solution is returned to a 300 ml four-necked flask equipped with a solvent recovery device, and 60 g of dimethylacetamide is added to raise the temperature. Distillation starts when the temperature reaches 163 ℃, but the temperature is 1
Dimethylacetamide was distilled off until the temperature reached 70 ° C, and then the mixture was kept under reflux for 5 hours.

After the reaction, the product is separated by precipitation in water. Then, it was purified by recrystallization from methanol and dried under reduced pressure to obtain a pale yellow powder.

This has a hydroxyl equivalent of 187 g / eq and a melting point of 293 ° C.
Elemental analysis results are C67.0%, H3.61%, N7.50%,
The following structure was obtained.

(Alkenyl etherification) In a 100 ml four-necked flask equipped with a thermometer, a condenser, and a stirrer, 7.48 g (0.04 equivalent) of the above amide imide compound, 60 g of dimethyl sulfoxide, 5.8 g of allyl bromide (0.048 mol)
Charge and dissolve. While keeping the temperature of the reaction system at 50 ° C, 28% sodium methoxide 8.49g (0.044mol) was charged under a nitrogen stream and kept at 50 ° C for 2 hours. After keeping the temperature at room temperature, dimethyl sulfoxide was distilled off under reduced pressure to about 80% of the charged amount, and then water 60
g was added for precipitation and filtration, and the filter residue was washed with an appropriate amount of water and dried under reduced pressure to obtain a yellowish gray powder.

This product had an allyl etherification rate of 98% and a melting point of about 80 ° C.

Example 2 (Synthesis of Imido Compound Containing Terminal Hydroxyl Group) A thermometer, a condenser, a nitrogen introducing tube, and a stirrer were attached.
In a 300 ml four-necked flask, 36.25 g (0.1125 mol) of benzophenone tetracarboxylic acid anhydride and 182.4 g of m-cresol
, And raise the temperature to 140 ° C. After the dissolution, 24.56 g (0.225 mol) of m-aminophenol was charged, the temperature was raised to 170 ° C and the temperature was kept at the same temperature for 6 hours. During this time, nitrogen is flown from the nitrogen introducing pipe at a flow rate of 10 liters / hour to distill off the produced water. After the reaction, the precipitate was washed with methanol, washed, and dried under reduced pressure to obtain a pale yellow powder.

This compound had a hydroxyl equivalent of 252 g / eq, a melting point of 300 ° C. or higher, and elemental analysis results were C68.71%, H3.34%, N5.63%, and the following structures were obtained.

(Alkenyl etherification) Into a 100 ml four-necked flask equipped with a thermometer, a condenser and a stirrer, 5.04 g (0.02 equivalent) of the above imide compound, 40 g of dimethyl sulfoxide and 2.90 g (0.024 mol) of allyl bromide are charged and dissolved. 28% sodium methoxide 4.24 g (0.022 mol) under nitrogen stream while maintaining the temperature of the reaction system at 50 ° C.
Incubate and incubate at 50 ° C for 3 hours. After heat retention, a post-treatment was carried out in the same manner as in Example 1 to obtain a yellowish gray powder.

This product had an allyl etherification rate of 100% and a melting point of about 210 ° C.

Claims (1)

[Claims] 1. The following general formula [In the formula, Ar ¹ represents a residue of benzene, Ar ² represents a residue of benzene, biphenyl or benzophenone,
X is -NHCO- or And R represents hydrogen or a lower alkyl group. ] The aromatic imide alkenyl ether shown by these.