JPH07116124B2 - Novel ether diamine and method for producing the same - Google Patents

Description

TECHNICAL FIELD The present invention relates to a novel ether diamine and a method for producing the same. More specifically, the compound of formula (I) obtained by reacting 4,4'-dihalogendiphenyl sulfone with 4- (4-aminophenoxy) -4'-hydroxybiphenyl in the presence of a base in an aprotic polar solvent. The present invention relates to a novel ether diamine.

The compound of the present invention has never been produced before, and its use is unknown.

However, due to its production, the monomer of heat-resistant polymer,
In particular, it is useful as a basic raw material for polyamide, polyimide, polyamino bismaleimide resin and the like.

(Prior Art) Conventionally, polyimide obtained by the reaction of tetracarboxylic dianhydride and diamine is known to have various excellent physical properties, particularly good heat resistance, and will be widely used in fields where further heat resistance is required in the future. It is expected to be done.

However, conventionally known polyimide resins have various problems such as those having excellent heat resistance are poor in workability, and those developed for the purpose of improving workability are conversely poor in heat resistance. ing.

For example, formula (II) Polyimide with a basic skeleton represented by (DuPont: trade name Kapton, Vespel) does not have a clear glass transition temperature and is a polyimide with excellent heat resistance, but it is processed when used as a molding material. However, it must be processed by using a technique such as sinter molding.

On the other hand, formula (III) Polysulfone having a basic skeleton represented by (US UCC
(Trade name, Udel Polysulfone, manufactured by the company) has a low glass transition temperature of 195 ° C. The glass transition temperature of the polyether sulfone represented by (ICI Co., Ltd., trade name Victorex Pess) is 225 ° C.
Although heat resistance is improved as compared with polysulfone, it is not satisfactory in heat resistance as compared with conventional polyimide.

(Problems to be solved by the invention) The object of the present invention is, in addition to the excellent heat resistance that the polyimide resin originally has, a novel compound that is a raw material of a polyimide resin that has excellent processability and can be used for multipurpose applications, That is, to provide an aromatic ether diamine.

(Means for Solving Problems) The present inventors have synthesized various diamines to achieve the above-mentioned problems, produced polyimide resins as these raw materials, and evaluated the performance thereof. , Formula (I) The present invention has been completed by finding that a polyimide resin made from a novel etherdiamine represented by the formula (4) shows excellent performance. That is, the polyimide resin composed of the novel ether diamine represented by the formula (I) and pyromellitic dianhydride has a glass transition temperature (Tg) of 288 ° C. and a melting point (Tm) of 4
It has a heat resistance of 48 ° C. and a 5% weight loss temperature in air of 521 ° C., which is extremely good in terms of moldability and thermal stability.

Therefore, the compound of the present invention is useful as a raw material for a polyimide resin having extremely excellent heat resistance.

The raw materials used in the method of the present invention are 4,4'-dihalogendiphenyl sulfone and 4- (4-aminophenoxy).
-4'-hydroxybiphenyl. The usage amount is 4-
(4-aminophenoxy) -4'-hydroxybiphenyl was added to 2,4'-dihalogendiphenylnulphone to 2
The molar amount is at least twice, preferably 2 to 3 times.

The 4,4'-dihalogenodiphenyl sulfone used in the method of the present invention includes 4,4'-dichlorodiphenyl sulfone, 4,4'-difluorodiphenyl sulfone, 4,4'-
Dibromodiphenyl sulfone, etc.
4'-dichlorodiphenyl sulfone is used.

4- (4-aminophenoxy) -4'-hydroxybiphenyl is 4-hydroxy- obtained by condensing 4,4'-dihydroxybiphenyl and p-chloronitrobenzene.
It can be easily produced by reducing 4 '-(4-aminophenoxy) biphenyl.

The base used in the method of the present invention is an alkali metal hydroxide, hydrogen carbonate or alkoxide, and specifically, potassium hydroxide, sodium hydroxide, lithium hydroxide, potassium carbonate, sodium carbonate, lithium carbonate. , Sodium hydrogen carbonate, potassium ethoxide, potassium isopropoxide, sodium methoxide, sodium ethoxide, lithium ethoxide and the like. This may be used alone or in combination of two or more kinds.

These bases are used in a molar amount of 2 times or more, preferably 2 to 3 times, the molar amount of 4,4'-dihalogenodiphenyl sulfone as a raw material. Next, an aprotic polar solvent is used as a reaction solvent in this method.

As the aprotic polar solvent, N-methylformamide, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, dimethylsulfone, sulfolane, 1-methyl-2-pyrrolidone, 1,3-
Examples thereof include dimethyl-2-imidazolidinone and hexamethyltriamide phosphate. The amount of these solvents used is not particularly limited, but usually, 1 to 10 times by weight of the raw material is sufficient. The reaction temperature is usually in the range of 100 to 240 ° C, preferably 120 to 200 ° C.

In the method of the present invention, quaternary ammonia salt, quaternary phosphonium salt, macrocyclic polyether such as crown ether, nitrogen-containing cyclic polyether such as cryptate,
A phase transfer catalyst such as nitrogen-containing chain polyether, polyethylene glycol and its alkyl ether, and copper powder and copper salt may be added as a reaction accelerator.

In a general embodiment of the process according to the invention, a predetermined amount of 4- (4-aminophenoxy) -4'-hydroxybiphenyl, base and solvent are charged and 4- (4-aminophenoxy) 4'- After making hydroxybiphenyl into an alkali metal salt, 4,4'-dihalogenodiphenyl sulfone is added and reacted, or 4,4 '
-All the raw materials including diphenyl sulfone may be added at the same time and the temperature may be raised as it is to react. Of course, it is not limited to these, and it can be implemented by other methods. When water is purified in the reaction system, as a method for removing it, a method of gradually removing it in the reaction system by aeration with nitrogen gas or a small amount of benzene, toluene, xylene, chlorobenzene, etc. A method of removing it outside the system by azeotropic distillation may be used. The end point of this reaction can be determined by thin layer chromatography or high performance liquid chromatography while observing the reduction of the raw material or unreacted intermediate (mono-substituted product).

After completion of the reaction, the reaction solution obtained by the above method is directly discharged to water or the like, or inorganic salts are removed by filtration, and then the solvent is concentrated to obtain a crude product. There is a method of recrystallizing the obtained crude product with a solvent or precipitating it as a mineral acid salt by adding a mineral acid such as hydrochloric acid to neutralize the product.

(Operation and Effect) The present invention provides a novel ether diamine and a method for producing them. The polyimide resin using the diamine of the present invention as a monomer is characterized by extremely good thermal stability and easy molding. That is, the novel etherdiamine of the present invention provides a compound useful as a raw material for a polyimide resin or a raw material for a polyimide resin, a bismaleimide resin or the like. In addition, these compounds were treated with 4,4'-dihalogenodiphenyl sulfone and 4- (4-aminophenoxy)-
The present invention provides a process which can be performed with high purity and good yield by reacting 4'-hydroxybiphenyl in an aprotic polar solvent in the presence of a base. The present invention has the industrial significance. Is a big one.

(Examples) Hereinafter, the present invention will be described in more detail with reference to Examples.

Example 1 A reaction flask equipped with a stirrer, a thermometer, and a cooling tube was added with 4-
87.35 g (0.315 mol) of (4-aminophenoxy) -4'-hydroxybiphenyl, 42.8 g of 96% potassium hydroxide (0.
73 mol), 1,3-dimethyl-2-imidazolidinone 262
Then, 20 g of toluene and 20 g of toluene were charged, the temperature was raised while nitrogen gas was being passed under stirring, and the water in the reaction system was removed by a water separator while the toluene was refluxed.

Next, after lowering the internal temperature to 100 ° C., 43.07 g (0.15 mol) of 4,4′-dichlorodiphenyl sulfone was added to 1,3-dimethyl-2.
-A solution dissolved in 86 g of imidazolidinone was added dropwise and the temperature was raised again to keep the internal temperature at 140-150 ° C. The reaction was completed at the same temperature for 4 hours. When the reaction solution was cooled and then discharged into methyl alcohol, crystals were precipitated. This was filtered and washed, and then recrystallized with o-dichlorobenzene to obtain white crystals.

Yield 99.1g (Yield 86.0%) mp 260-262 ℃ Elemental analysis (C ₄₈ H ₃₆ O ₆ N ₂ S) C H N S Calculated value (%) 74.99 4.72 3.66 4.17 Analytical value (%) 74.58 4.50 3.38 4.55 IR (KBr, cm ^-1 : 3450,3350: Amino group 1240: Ether bond 1150: Sulfone MS (FD method): 768 (M ⁺ )

Claims (2)

[Claims] 1. A formula (I) A new ether diamine represented by. 2. A formula (4) characterized in that 4,4'-dihalogendiphenyl sulfone and 4- (4-aminophenoxy) -4'-hydroxybiphenyl are reacted in an aprotic polar solvent in the presence of a base. I) A method for producing a novel ether diamine represented by: