JPH0737448B2 - Aromatic diamine containing pyridine ring and method for producing the same - Google Patents

Description

TECHNICAL FIELD The present invention relates to an aromatic diamine containing a pyridine ring and a method for producing the same.

The aromatic diamine containing a pyridine ring of the present invention has no known uses because there is no example produced before. However, these aromatic diamines are compounds expected to be usable as raw materials for polyimide resins, polyamide resins and bismaleimide resins, and as curing agents for epoxy resins.

(Technical background of the invention) Aromatic diamine is used as a raw material monomer of a polyamide resin or a polyimide resin, for example, an aromatic polyimide resin made from 4,4'-diaminodiphenyl ether as a raw material (Du'pout, trade name Kapton, Vespel) is known.

Although this polyimide resin has excellent heat resistance, it has a drawback that it is difficult to process when used as a molding material. As described above, many of the polyimide resins developed so far have excellent properties, but they have excellent heat resistance but are poor in processability, and resins developed for the purpose of improving processability are heat resistant. There were merits and demerits in performance such as poor performance.

For example, 2,2-bis (4- (3-aminophenoxy) phenyl) propane or 4,4′-bis (3-amino) is used as a polyimide resin containing aromatic long-chain etherdiamine as a raw material monomer. In addition to the excellent heat resistance, those using phenoxy) biphenyl as a raw material monomer,
We filed a patent application to find out that it is a polyimide resin with high heat resistance and excellent workability (Japanese Patent Application No. 60-186610, 61-
046369).

Furthermore, the polyimide resin containing 2,6-bis (3-aminophenoxy) pyridine as a raw material monomer has excellent heat resistance as an aromatic polyimide resin containing a pyridine ring, and since it is thermoplastic, it has good processability and heat resistance. We filed a patent application for having excellent adhesiveness (Japanese Patent Application No. 61-02693).
6). Since this polyimide resin has a pyridine ring in the main chain skeleton, it is expected that conductivity is exhibited by forming a metal chelate by doping with a metal ion.

(Problems to be Solved by the Invention) The problem to be solved by the present invention is that the aromatic long-chain ether diamine has excellent properties and the aromatic diamine having a pyridine ring in the main chain skeleton has not been conventionally produced. An aromatic diamine that can be expected as a raw material monomer for a polyimide resin having both of the above and a method for producing the same.

(Means for Solving Problems) The inventors of the present invention have earnestly studied to solve such a problem.

as a result General formula (II) (Where X is In which Y represents a chlorine or bromine atom) and a bis (6-halogeno-2-pyridyloxy) compound represented by the formula:
It was characterized by reacting in an aprotic polar solvent.

The compound of the present invention can be produced as follows.

The bis (6-halogeno-2-pyridyloxy) compound used as a material can be produced by reacting 2,6-dihalogenoporidine with a biphenol in the presence of a base in a solvent (Japanese Patent Application No. 61- 165471).

The starting material used is 3- to 4-aminophenol in an amount of 2 to 5 times, preferably 2 to 3 times the mol of the bis (6-halogeno-2-pyridyloxy) compound.

The base used is an alkyl metal hydroxide, carbonate, bicarbonate or alkoxide, and examples thereof include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, lithium carbonate and bicarbonate. Examples include sodium carbonate, potassium bicarbonate, potassium ethoxide, potassium isopropoxide, sodium methoxide, sodium ethoxide and lithium ethoxide. Industrially, hydroxides and carbonates of potassium and sodium are used. These may be used alone or in combination of two or more kinds.

The amount of these bases used may be equivalent to or more than the aminophenol, preferably 1.1 to 1.5 equivalents.

Next, the reaction solvent in this method is used, usually an aprotic polar solvent.

Examples of the aprotic polar solvent include N-methylformamide, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone and 1,3-dimethyl-
Examples thereof include 2-imidazolidinone, hexamethyltriamide phosphate, dimethyl sulfoxide, dimethyl sulfone and sulfolane.

The amount of these solvents used is not particularly limited, but usually 1 to 10 times by weight of the raw material is sufficient.

In these reactions, quaternary ammonium salts, quaternary phosphorus salts, macrocyclic polyethers such as crown ethers, nitrogen-containing macrocyclic polyethers such as cryptate, nitrogen-containing chain polyethers, polyethylene glycol and its alkyl ethers are used. Such a phase transfer catalyst, copper powder and copper salt may be added as a reaction accelerator.

In carrying out the reaction, there is no particular limitation such as a charging method of raw materials, but for example, (1) a method in which an alkali metal salt of 3- or 4-aminophenol is prepared in advance,
(2) The reaction proceeds by any method such as a method in which all the raw materials are charged from the beginning and reacted, and there is no particular limitation. When water is generated in the reaction system, it can be removed by ventilating nitrogen gas to gradually remove it out of the reaction system, or by using a small amount of benzene, toluene, xylene, chlorobenzene, etc. A method of removing it to the outside of the system by boiling is used.

The reaction temperature is usually in the range of 100 to 240 ° C, preferably 120 to 2
It is in the range of 00 ° C. The end point of the reaction can be determined by thin layer chromatography, high performance liquid chromatography or the like.

After the reaction is complete, the product is concentrated or discharged as it is to water to obtain the desired product.

(Action and Effect) According to the present invention, an aromatic azimine containing a pyridine ring can be industrially easily produced by reacting a bis (6-halogeno-2-pyridyloxy) compound with an aminophenol. This compound can be expected to have excellent heat resistance, adhesiveness and processability as a raw material monomer for polyimide resin or polyamide resin.

(Examples) The present invention will be described in more detail with reference to Examples.

Example 1 3-in a 200 ml flask equipped with a stirrer and a water separator
Aminophenol 22.3 g (0.205 mol), 96% flame sodium hydroxide 9.2 g (0.22 mol), N, N-dimethylformamide 100 ml and benzene 10 ml were charged, and the temperature was raised while agitating nitrogen gas. The water in the reaction system was removed by a water separator under the reflux condition of benzene. Next, after lowering the internal temperature to 80 ° C or lower, 1,4-bis (6-chloro-
33.3 g (0.1 mol) of 2-pyridyloxy) benzene was charged and the temperature was raised again to keep the internal temperature at 140 to 150 ° C. At the same temperature
The reaction was carried out for 13 hours and the reaction was completed. After cooling the reaction solution, water 500m
When discharged to l, brown crystals were precipitated. This was filtered, washed with water and dried to obtain crude 1,4-phenylenedioxy-bis [6-
(3-Aminophenoxy) -2-pyridine] (39.2 g) was obtained (yield 82.0%).

To this crude crystal, 20.8 g of 35% hydrochloric acid aqueous solution, 200 g of water and 200 g of isopropyl alcohol are added and dissolved by heating. After that, cool to 20 to 25 ° C, filter the deposited results, and
When dissolved in a hydrated isopropyl alcohol solution and neutralized with aqueous ammonia, a pale brown crystal was precipitated. This is filtered and dried to give pure 1,4-phenylenedioxy-bis [6-
(3-Aminophenoxy) -2-pyridine] was obtained. The melting point was 147-148 ° C. The results of elemental analysis, IR spectrum and mass spectrum are as follows.

Elemental analysis (C ₂₈ H ₂₂ N ₄ O ₄ ) C H N calculated value (%) 70.29 4.60 11.72 Analytical value (%) 70.55 4.35 11.63 IR spectrum (MBr disk cm ⁻¹ ) 3420, 3340 (amino group), 1220 ( Ether bond) MS spectrum (M / e) 478 (M ⁺ ) 239 Example 2 In a 200 ml flask equipped with a stirrer, 22.3 g (0.205 mol) of 4-aminophenol and 1,4-bis (6-chloro-2) were used.
-Pyridyloxy) benzene 33.3 g (0.1 mol), anhydrous potassium carbonate 20.7 g (0.15 mol) and 1,3-dimethyl-2
-Imidazolidinone (100 ml) was charged, and the mixture was reacted for 12 hours at an internal temperature of 150 to 160 ° C while agitating nitrogen gas.

After the completion of the reaction, the inorganic salt was removed by filtration, and the solvent was recovered by concentration under reduced pressure. 35% hydrochloric acid aqueous solution 20.8 g, water 200 g and isopropyl alcohol 200 g were added to the residual brown oily substance.
Add and heat to dissolve. 35% hydrochloric acid aqueous solution 20.8
After adding g, the mixture was cooled to 20 to 25 ° C, and the precipitated crystals were separated by filtration.
The crystals were dissolved in a 50% hydrous isopropyl alcohol solution and then neutralized with aqueous ammonia to precipitate light brown crystals. The crystals were separated by filtration and then recrystallized from toluene to give white needle crystals of 1,4-phenylenedioxy-bis [6- (4
-Aminophenoxy) -2-pyridine] 32.5 g was obtained (yield 68.0%).

The melting point was 194-195 ° C. The results of elemental analysis, IR spectrum and mass spectrum are as follows.

Elemental analysis (C ₂₈ H ₂₂ N ₄ O ₄ ) C H N calculated value (%) 70.29 4.60 11.72 Analytical value (%) 70.50 4.52 11.97 IR spectrum (MBr disk cm ⁻¹ ) 3410, 3350 (amino group), 1220 ( Ether bond) MS spectrum (M / e) 478 (M ⁺ ) 239 Example 3 In the reaction of Example 2, the starting material was 3-aminophenol 22.3.
g (0.205 mol), anhydrous sodium carbonate 15.9 g (0.15 mol), 4,4'-bis (6-chloro-2-pyridyloxy) biphenyl 40.9 g (0.1 mol), and N, N- as a solvent.
Using 100 ml of dimethylacetamide, the reaction is 150-160 ℃
The same procedure was repeated except that the reaction was performed for 12 hours in 2-methoxyethanol, and recrystallization was performed to give white crystals of 4,4′-bisphenylenedioxy-bis [6- (3-aminophenoxy) -2-pyridine] 39.0 g was obtained (70.4% yield).

The melting point was 162-163.5 ° C. The results of elemental analysis, IR spectrum and mass spectrum are as follows.

Elemental analysis (C ₃₄ H ₂₆ N ₄ O ₄ ) C H N calculated value (%) 73.65 4.69 10.11 Analytical value (%) 73.46 4.82 10.29 IR spectrum (MBr disk cm ⁻¹ ) 3460, 3380 (amino group), 1225 ( Ether bond) MS spectrum (M / e) 554 (M ⁺ ) 277,185 Example 4 In the reaction of Example 1, the starting material was 4-aminophenol 22.3.
g (0.205 mol), 96% flake potassium hydroxide 12.8g
(0.22 mol), 4,4'-bis (6-chloro-2-pyridyloxy) biphenyl 40.9 g (0.1 mol) and the solvent were replaced with 100 ml of sulfolane, and the reaction was carried out at 140 to 150 ° C for 16 hours. went. After the reaction is complete, cool the reaction mixture and wash with water.
When discharged to 500 ml, brown crystals were precipitated. This was filtered, washed with water and dried to obtain crude 4,4'-biphenylenedioxy-
Bis [6- (4-aminophenoxy) -2-pyridine]
47.1 g was obtained (yield 85.0%).

20.8 g of 35% hydrochloric acid aqueous solution, 200 g of water, and 200 g of 2-methoxyethanol are added to the crude crystals to dissolve them by heating. 20 g of sodium chloride was added to this, cooled to 20 to 25 ° C., and the precipitated crystals were separated by filtration, dissolved in a 50% water-containing 2-methoxyethanol solution and neutralized with aqueous ammonia to precipitate light brown crystals. This was filtered and dried to obtain pure 4,4'-biphenylenedioxy-bis [6- (4-aminophenoxy) -2-pyridine]. The melting point was 118.5-120 ° C. The results of elemental analysis, IR spectrum and mass spectrum are as follows.

Elemental analysis (C ₃₄ H ₂₆ N ₄ O ₄ ) C H N calculated value (%) 73.65 4.69 10.11 Analytical value (%) 73.40 4.79 10.32 IR spectrum (MBr disk cm ⁻¹ ) 3420, 3360 (amino group), 1220 ( Ether bond) MS spectrum (M / e) 554 (M ⁺ ) 277,185 Example 5 In the reaction of Example 2, starting material was 3-aminophenyl 22.3 g.
(0.205 mol), 2,2-bis [4- (6-chloro-2-pyridyloxy) phenyl) propane 45.1 g (0.1 mol),
20.7 g (0.15 mol) of anhydrous potassium carbonate as the base, and 100 ml of N, N-dimethylformamide as the solvent were added, and the reaction was carried out at 14
The same procedure was repeated except that the reaction was carried out at 0 to 150 ° C for 14 hours, and recrystallized from a mixed solvent of 2-methoxymethanol and isopropyl alcohol to give 2,2-bis {4- [6-3-aminophenoxy) as white needle crystals. 39.9 g of crystals of 2-pyridyloxy] phenyl} propane were obtained (yield 66.9%). Melting point is 139 ~
It was 140.5 ° C.

The results of elemental analysis, IR spectrum and mass spectrum are as follows.

Elemental analysis (C ₃₇ H ₃₂ N ₄ O ₄ ) C H N calculated value (%) 74.50 5.37 9.40 Analytical value (%) 74.35 5.58 9.30 IR spectrum (MBr disk cm ⁻¹ ) 3430, 3370 (amino group), 1220 ( Ether bond) MS spectrum (M / e) 596 (M ⁺ ) 298 Example 6 In the reaction of Example 1, 22.3 g of 4-aminophenol was used as a raw material.
(0.205 mol), 2,2-bis [4- (chloro-2-pyridyloxy) phenyl] propane 45.1 g (0.1 mol), base is 96% flake potassium hydroxide 12.8 g (0.22 mol) and solvent is N -Change to 100 ml of methylpyrrolidone and repeat the reaction
The same procedure was repeated except that the procedure was carried out at 50 to 160 ° C. for 12 hours to obtain 48.3 g of crude 2,2-bis {4- [6- (4-aminophenoxy) 2-pyridyloxy] phenyl} propane (yield 81.0
%). The crude crystals were recrystallized with 2-methoxyethanol to obtain slightly brown crystals. The melting point was 118-120 ° C. The results of elemental analysis, IR spectrum and mass spectrum are as follows.

Elemental analysis (C ₃₇ H ₃₂ N ₄ O ₄ ) C H N calculated value (%) 74.50 5.37 9.40 Analytical value (%) 74.89 5.51 9.28 IR spectrum (MBr disk cm ⁻¹ ) 3410, 3360 (amino group), 1220 ( Ether bond) MS spectrum (M / e) 596 (M ⁺ ) 298

Claims (1)

[Claims] 1. General formula (II) (Where X is In which Y represents a chlorine or bromine atom) and a bis (6-halogeno-2-pyridyloxy) compound represented by the formula:
General formula (I) characterized by reacting in an aprotic polar solvent (Where X is And the substitution position of the amino group is 3 with respect to the ether bond.
The method for producing an aromatic diamine containing a pyridine ring represented by -or 4-position).