JP2524323B2 - New diimidedicarboxylic acid and its production method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial field of use] The present invention relates to a novel diimidedicarboxylic acid useful as a raw material for polyesterimide and the like and a method for producing the same.

[Problems to be Solved by Conventional Techniques and Inventions] Conventionally, diimidedicarboxylic acid has been used as a raw material for producing polyesterimide, and for example, the one represented by the following formula in U.S. Pat. Proposed.

However, this diimidodicarboxylic acid does not show a melting point even at 450 ° C. and is inferior in meltability, so that it is not suitable for use in melt copolymerization.

[Means for Solving Problems] The present inventor has solved the above problems in the past, found a novel diimidedicarboxylic acid suitable for melt copolymerization, and completed the present invention.

That is, the present invention is [In the formula, R ¹ and R ² represent the same or different kinds of halogen atoms or alkyl groups having 1 to 6 carbon atoms, and m and n are 1 or 2
Indicates. ] To provide a novel diimidedicarboxylic acid represented by [In the formula, R ¹ and R ² represent the same or different kinds of halogen atoms or alkyl groups having 1 to 6 carbon atoms, and m and n are 1 or 2
Indicates. ] A 1,4-diaminobenzene derivative represented by the above formula is reacted to provide a process for producing the first novel diimidedicarboxylic acid of the present invention represented by the above formula [I].

In the above formula [I], R ¹ and R ² each represent a halogen atom such as chlorine, fluorine and bromine, or an alkyl group having 1 to 6 carbon atoms such as a methyl group and an ethyl group. Here, R ¹ and R ² may be the same or different. Moreover, m and n have shown 1 or 2, respectively.

Specific examples of the novel diimidedicarboxylic acid represented by the formula [I] include 1,4-bis [(4-carboxy) phthalimide] -2,5-dichlorobenzene and 1,4-bis [(4-carboxy). Phthalimido] -2,6-dichlorobenzene, 1,4-bis [(4-carboxy) phthalimido] -2,5-dimethylbenzene, 1,4-bis [(4-carboxy) phthalimido] -2-methyl-5 Examples include chlorobenzene. Among these, preferred is 1,4-bis [(4-carboxy) phthalimide]-
They are 2,5-dimethylbenzene and 1,4-bis [(4-carboxy) phthalimide] -2,5-dichlorobenzene.

The first novel diimidedicarboxylic acid of the present invention represented by the above formula [I] can be produced by various methods, and the efficient second method is the second method of the present invention.

That is, the second aspect of the present invention is trimellitic anhydride,
It is characterized by reacting a 1,4-diaminobenzene derivative represented by the above formula [II].

Where trimetic anhydride has the formula Is represented by.

In the second aspect of the present invention, the 1,4-diaminobenzene derivative represented by the above formula [II] is used together with this trimellitic anhydride. In the formula [II], R ¹ , R ² , m, and n are as described in the description of the formula [I].

As the 1,4-diaminobenzene derivative represented by the above formula [II], 1,4-diamino-benzene derivative is easily available.
2,5-dimethylbenzene, 1,4-diamino-2,5-dichlorobenzene, 1,4-diamino-2-methyl-5-chlorobenzene, 1,4-diamino-2,6-dichlorobenzene, etc. are used. Is preferred.

The reaction conditions in this case are not particularly limited, but the above formula [I
It is preferable to react approximately twice the molar amount of trimellitic anhydride with respect to the 1,4-diaminobenzene derivative represented by [I]. The reaction temperature may be 150 to 180 ° C., the pressure may be normal pressure or pressurized state, and the reaction time is usually 5 to 10 hours. The solvent used in the reaction is a polar solvent such as dimethylacetamide, dimethylformamide, dimethylsulfoxide, N-methylformamide, N-methyl-2-pyrrolidone, sulfolane, N, N, N ', N'-tetramethylurea, and nitrogen. It is preferably carried out in an atmosphere of an inert gas such as argon.

As described above, the first novel diimidedicarboxylic acid of the present invention can be produced.

[Examples] Next, examples of the present invention will be shown, but the present invention is not limited thereto as long as the scope of the present invention is not exceeded.

Example 1 A trimellitic anhydride was placed in a flask having an inner volume of 1 equipped with a stirrer, a reflux condenser, and an argon gas blowing tube.
76.8 g (0.4 mol), 1,4-diamino-2,5-dimethylbenzene 27.2 g (0.2 mol) and dimethylacetamide 500 ml as a solvent were added, and the mixture was stirred at room temperature while blowing an argon gas until a homogeneous solution was formed. Next, the temperature was raised to 170 ° C. and the reaction was carried out for 8 hours while stirring. The obtained product was poured into water of 3, the precipitate was separately collected, and washed with water and methanol, respectively, to obtain 86.5 g of white crystals. The melting point of the obtained compound was 430 ° C., and the results of its elemental analysis were as follows.

Further, the infrared absorption spectrum analysis of this compound, absorption by the benzene ring in a position of 1580 cm ^-1 and 1490cm ^-1, absorption by carbonyl group at the position of 1650cm ^-1, 1780~
Absorption by imide group was observed at a position of 1680 cm ^-1 and 720 cm ^-1. From the above, this compound was confirmed to have the structure shown below.

Example 2 In Example 1, 1,4-diamino-2,5-dimethylbenzene was replaced by 1,4-diamino-2,5-dichlorobenzene.
93.2 g of white crystals was obtained in the same manner as in Example 1 except that 35.4 g (0.2 mol) was used. The melting point of the obtained compound is 420 ° C.
The results of the elemental analysis were as follows.

Further, the infrared absorption spectrum analysis of this compound, absorption by the benzene ring in a position of 1580 cm ^-1 and 1490cm ^-1, absorption by carbonyl group at the position of 1650cm ^-1, 1780~
Absorption by imide group was observed at a position of 1680 cm ^-1 and 720 cm ^-1. From the above, this compound was confirmed to have the structure shown below.

Application Example 1 4.88 g of 1,4-bis [(4-carboxy) phthalimide] -2,5-dimethylbenzene obtained in Example 1 was added to a reactor equipped with a stirrer and an argon gas blowing tube.
01 mol), 4,4'-biphenol diacetate 2.60 g (0.
01 mol), p-acetoxybenzoic acid 12.6 g (0.07 mol)
Then, 3.84 g of polyethylene terephthalate (0.02 mol in terms of monomer unit) was added, the temperature was raised to 280 ° C. under an argon gas stream, the temperature was maintained for 1 hour, and the acetic acid produced was distilled off. Next, the pressure inside the reactor was reduced to 1 mmHg, and the reaction was carried out at 280 ° C. for 2 hours to obtain a polymer.

The polymer obtained here had a reduced viscosity [η _SP / c] (hereinafter, the same) at 0.6 ° C. of a solution having a concentration of 0.2 g / dl in which p-chlorophenol was the solvent was 0.65 dl / g. Also,
Infrared absorption spectrum analysis of the results, 1580 cm ^-1 and 1490cm ^-1
Absorption by the Bensen ring at the position of 1780-1680 cm ^-1
And absorption by the imide group was observed at the position of 720 cm ^-1 .
From these, it was confirmed that this polymer was composed of the following repeating units.

Furthermore, it was confirmed that this polymer exhibited liquid crystallinity at 250 ° C. or higher under a polarizing microscope.

Next, this polymer shows excellent performance as a fiber, and a yarn diameter of 30 mm spun at 320 ° C. with a spinning nozzle having an inner diameter of 1 mm.
The mechanical strength measured according to JIS-L-1069 with respect to the μm fiber was as follows.

Tensile strength 0.43 GPa Tensile modulus 50 GPa Application Example 2 In Application Example 1, 1,4-bis [(4-carboxy)
Phthalimide] -2,5-dimethylbenzene was replaced with 1,4-bis [(4-carboxy) phthalimido] -2,5-dichlorobenzene 5.25 g (0.01 mol) obtained in Example 2 and applied. A polymer was obtained in the same manner as in Example 1. The reduced viscosity [η _SP / c] of this polymer was 0.75 dl / g, and the result of infrared absorption spectrum analysis was the same as in Application Example 1. The mechanical strength of a fiber having a yarn diameter of 30 μm obtained by spinning this polymer at 300 ° C. was as follows.

Tensile strength 0.33 GPa Tensile modulus 48 GPa Reference Example 1 1,4-bis [(4-carboxy) phthalimide] -2,5-dimethylbenzene used in Application Example 1 was replaced by a known diimidedicarboxylic acid 1, The same operation as in Application Example 1 was carried out using 4.56 g (0.01 mol) of 4-bis [(4-carboxy) phthalimide] benzene, but it did not melt at 280 ° C and formed a uniform liquid phase with the comonomer. There wasn't. The obtained product was inhomogeneous and did not exhibit thermoplasticity, and thus was difficult to mold.

[Effects of the Invention] The novel diimidedicarboxylic acid of the present invention is excellent in melt polymerizability as compared with the known diimidedicarboxylic acid, and its industrial value as a raw material for polyesterimide and the like is extremely large. Further, according to the production method of the present invention, the above diimidedicarboxylic acid can be efficiently produced.

Claims (2)

(57) [Claims] 1. A formula [In the formula, R ¹ and R ² represent the same or different kinds of halogen atoms or alkyl groups having 1 to 6 carbon atoms, and m and n are 1 or 2
Indicates. ] The new diimide dicarboxylic acid represented by these. 2. A trimellitic anhydride and a formula [In the formula, R ¹ and R ² represent the same or different kinds of halogen atoms or alkyl groups having 1 to 6 carbon atoms, and m and n are 1 or 2
Indicates. ] The formula characterized by reacting a 1,4-diaminobenzene derivative represented by [In the formula, R ¹ and R ² represent the same or different kinds of halogen atoms or an alkyl group having 1 to 6 carbon atoms, and m and n represent 1 or 2. ] The manufacturing method of the novel diimide dicarboxylic acid represented by these.