JPH0637444B2 - 4,4'-bis (3-aminophenoxy) biphenyl - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION Industrial Field of the Invention The present invention relates to a novel aromatic ether diamine, 4,
It relates to 4'-bis (3-aminophenoxy) biphenyl.

(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 are poor in workability if they have excellent heat resistance, and conversely, those developed for the purpose of improving workability are inferior in heat resistance and solvent resistance. Have a point. For example, equation (2) Polyimide resin consisting of the basic skeleton represented by (Dupont
Company name, Kapton.Vespel) does not have a clear glass transition temperature and is excellent in heat resistance but inferior in processability, and when used as a molding material, a method such as sinter molding must be used. Cannot be processed. Further, in recent years, because of its heat resistance and insulating properties, polyimide resin has been used as a base material for electric and electronic parts, but the polyimide resin represented by the formula (2) has high water absorption and is a material for electric and electronic parts. It has a drawback that it has an adverse effect on dimensional stability, insulation, and solder heat resistance, which are important factors when used as. Also,
Formula (3) The polyetherimide resin having a basic skeleton represented by GE (trade name ULTEM manufactured by GE) has excellent processability, but has a low glass transition temperature of 217 ° C., is poor in heat resistance, and is a halogen such as methylene chloride. It has a drawback that it is soluble in a compounded hydrocarbon solvent.

(Problems to be Solved by the Invention) The object of the present invention is to have excellent workability and heat-resistant adhesiveness in addition to the excellent heat resistance originally possessed by a polyimide resin, low water absorption, and good transparency. It is intended to provide a novel compound as a raw material of a polyimide resin that can be used for multipurpose purposes, that is, an aromatic ether diamine.

(Means for Solving Problems) The inventors of the present invention have synthesized various kinds of diamines, manufactured polyimide resins using them as raw materials, and evaluated their performances in order to achieve the above-mentioned problems. As a result, the formula
For the first time, 4,4'-bis (3-aminophenoxy) biphenyl represented by (1) was produced, and this compound was excellent in heat resistance, processability, transparency and low in a polymer with tetracarboxylic dianhydride. It has been found that the novel aromatic ether diamine having water absorbency is preferable as a heat resistant resin raw material.

That is, the present invention is 4,4'-bis (3-aminophenoxy) biphenyl, which is a novel aromatic ether diamine.

Heretofore, in the aromatic nitro compound, many examples have been known regarding the reaction of substituting the nitro group of the compound activated by the electron-withdrawing group at the o- or p-position with a phenol. However, regarding the reaction of an unactivated nitro group such as m-dinitrobenzene, m-dinitrobenzene is reacted with an alkali metal phenoxide in a polar organic solvent in the presence of a macrocyclic polyether to give 3- Only a method for producing nitrodiphenyl ether is known (Japanese Patent Laid-Open No. 54-39030). 2 more
An aromatic ether diamine such as 4,4'-bis (3-aminophenoxy) biphenyl is prepared by condensing 4,4'-dihydroxybiphenyl having one hydroxyl group and two molecules of m-dinitrobenzene. There is no known method, and of course the compound itself has never been known.

The present inventors have investigated 4,4 ′ in the synthesis study of heat-resistant resin.
-Dihydroxyphenyl and m-dinitrobenzene can be reacted in the presence of a base in an aprotic polar solvent to produce 4,4'-bis (3-nitrophenoxy) biphenyl in good yield, which can be further reduced By doing 4,
We have succeeded in synthesizing 4'-bis (3-aminophenoxy) biphenyl. Then, a polymer was produced using this compound as a raw material, and it was confirmed that this polymer had extremely excellent performance. That is, it was confirmed that this compound has a high degree of usefulness, and the object of the present invention could be achieved.

The raw materials used to prepare the compounds of the present invention are 4,4'-
Dihydroxybiphenyl and m-dinitrobenzene are used, and the amount thereof is not particularly limited, but the amount of m-dinitrobenzene is usually 1.5 to 3 times mol with respect to 4,4'-dihydroxybiphenyl.

The condensation reaction between 4,4'-dihydroxybiphenyl and m-dinitrobenzene is carried out in the presence of a base in an aprotic polar solvent.

This condensation reaction gives 4,4'-bis (3-nitrophenoxy) biphenyl, which is then reduced to give 4,4'-bis (3-nitrophenoxy) biphenyl.
4'-Bis (3-aminophenoxy) biphenyl is obtained.

A base is used in the condensation reaction. For example, alkali metal oxides, hydroxides, carbonates, hydrogen carbonates, hydrides and alkoxides are used, but usually potassium carbonate,
Sodium carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate and the like are often used. The amount of base is usually 4,
1 to 5 times mol relative to 4'-dihydroxybiphenyl,
It is preferably 1.5 to 3 times by mole.

During this reaction, quaternary ammonium salt, quaternary phosphorus salt, macrocyclic polyether such as crown ether, nitrogen-containing macrocyclic polyether such as clibutate, nitrogen-containing chain polyether, polyethylene glycol and its alkyl ether Such a phase transfer catalyst, copper powder and copper salt may be added as a reaction accelerator.

An aprotic polar solvent is used as the reaction solvent. For example, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, 1-methyl-2-pyrrolidinone or 1,3-dimethyl-2-imidazolidinone are used. These solvents are usually used in an amount of 1 to 10 times the weight of the raw materials.

The reaction procedure is usually carried out by a method in which all raw materials including m-dinitrobenzene are initially charged and reacted as they are.

The reaction temperature is 100 to 240 ° C., preferably 120 to 1
The temperature is in the range of 80 ° C., and the reaction time is in the range of 5 to 30 hours. After completion of the reaction, the solvent is distilled off, or the reaction solution is directly discharged into water to obtain a crude product of the target product. Although this crude product can be purified by recrystallization or the like, it is usually subjected to the reduction reaction as it is. The reduction reaction is not particularly limited, and usually a method of reducing a nitro group to an amino group (for example, New Experimental Chemistry Course, Volume 15, Oxidation and Reduction [I
I] and Maruzen (1977)) can be applied, but industrially catalytic reduction or hydrazine reduction is preferable. As an example of catalytic reduction, a reducing catalyst such as a metal catalyst such as nickel, palladium or platinum, a supported catalyst, or a Raney catalyst such as nickel or copper is used as a raw material for 4,4′-bis (3-nitrophenoxy) biphenyl. Then, the reduction reaction is carried out using 0.01 to 10% by weight of the metal, therefore, 2 to 8% by weight when used in a metal state, and 0.1 to 5% by weight when supported on a carrier.

As the solvent used in the reduction reaction, those inert to the reaction such as methanol, ethanol, isopropyl alcohol and methyl cellosolve can be used.

The reaction temperature is not particularly limited. Generally 20-200
The range of ° C, especially 20 to 100 ° C is preferable. The reaction pressure is usually from atmospheric pressure to about 50 kg / cm ^{2 -G} .

On the other hand, to give an example of hydrazine reduction,
Usually, the reduction reaction is carried out using 1.2 to 2 times the physical quantity.

As the catalyst, a metal catalyst generally used for catalytic reduction can be used. A catalyst in which activated carbon adsorbs palladium / carbon, platinum / carbon or ferric chloride is particularly preferable. The amount used is usually 4,
It is in the range of 0.01 to 30% by weight as a metal based on 4'-bis (3-nitrophenoxy) biphenyl.

As the reaction solvent, the same solvent as in the case of catalytic reduction can be used. The reaction temperature is not particularly limited and is generally in the range of 20 to 150 ° C, particularly preferably 40 to 100 ° C.

After completion of the reaction, the reaction solution is heated to remove the catalyst, and then the solvent is distilled off if necessary to obtain a desired crude product of 4,4′-bis (3-aminophenoxy) biphenyl. This crude product can be purified by recrystallisation or isolation as the hydrochloride salt.

The novel aromatic ether diamine of the present invention can be obtained by the above method.

The aromatic ether diamine of the present invention can be polymerized with one or more tetracarboxylic acid dianhydrides to form a polyamic acid, and then cyclized and dehydrated to obtain a polyimide.

The obtained polymer has extremely excellent processability and heat-resistant adhesiveness.

Such performance shows that a polymer composed of 4,4 ′-(4-aminophenoxy) biphenyl and pyromellitic dianhydride having different diamine substitution positions from the compound of the present invention has a clear glass transition temperature. In comparison with the fact that it shows almost no adhesive strength, it has a remarkable difference in effect.

In the case of 4,4'-bis (4-aminophenoxy) biphenyl, even a polymer with benzophenonetetracarboxylic dianhydride does not have a clear glass transition temperature, has poor adhesive strength, and is inferior in processability.

From the compound of the present invention as a raw material, a polymer having the repeating unit of the formula (2), particularly polyimide has heat resistance peculiar to conventional polyimide, while being thermoplastic, processability and heat-resistant adhesiveness Among them, one of them is a polyimide resin having high heat resistance and capable of being melt-molded. Further, it has low water absorption, and in view of the excellent workability described above, it is widely used as a space / aircraft base material, electric / electronic component base material, and further as a heat resistant adhesive. .

(Action and Effect) 4,4 ′ which is the novel aromatic ether diamine of the present invention
-Bis (3-aminophenoxy) biphenyl is 4,
It can be industrially easily produced by the condensation and reduction reaction of 4'-dihydroxybiphenyl and m-dinitrobenzene.
Further, when this compound is polymerized with tetracarboxylic dianhydride, a novel polymer is obtained, and this polymer has excellent heat resistance, processability, transparency, low water absorption and adhesive ability. There is. That is, the compound of the present invention can be widely used as a resin raw material in a field in which heat resistance is required in the future.

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

Example 1 3 186 g (1.0 mol) of 4,4'-dihydroxybiphenyl and 43 m-dinitrobenzene in a glass reaction vessel.
8 g (2.6 mol), potassium carbonate 363 g and N, N
-Add 2,000 ml of dimethylformamide and add 145-1
React for 16 hours at 50 ° C. After completion of the reaction, the reaction mixture is cooled to remove KNO ₂ , then the solvent of the liquid is distilled off under reduced pressure, cooled to 65 ° C., and 2000 ml of methanol is charged and stirred for 1 hour. Separate crystals, wash with water, wash with methanol,
It was dried to obtain brown crystals of 4,4'-bis (3-nitrophenoxy) biphenyl. Yield 426g (Yield 99.5
%) Then, in a glass reaction vessel, crude 4,4'-bis (3
-Nitrophenoxy) biphenyl 100 g (0.23 mol), activated carbon 10 g, ferric chloride hexahydrate 1 g and methyl cellosolve 500 ml are charged, and the mixture is stirred under reflux for 30 minutes. Then, at 70-80 ° C, 46 g of hydrazine hydrate
(0.92 mol) is added dropwise over 3 hours. After dropping, 7
The reaction was complete after stirring at 0-80 ° C. for 5 hours. After cooling, the catalyst was removed by passing it, which was discharged into 500 ml of water and the crystals were passed through. To this, 48% of 35% hydrochloric acid and 50%
When 540 ml of isopropyl alcohol (IPA) / water was added and dissolved by heating, the mixture was allowed to cool, and 4,4'-bis (3-aminophenoxy) biphenyl hydrochloride was precipitated. After this, 540 ml of 50% IPA / water was added and dissolved by heating. After addition of 5 g of activated carbon, the mixture was neutralized with aqueous ammonia, and the crystals were washed with water, dried and dried to give 4,4'-bis (3-amino). Phenoxy) biphenyl was obtained. Yield 72.0g (Yield 85
%) Colorless crystals mp. 144-146 ° C Purity 99.6% (by high performance liquid chromatography) MS: 368 (M ⁺ ), 340, 184 IR (KBr, cm ^-1 ): 3400 and 3310 (NH ₂ group), 1
240 (ether bond) Example 21 The crude 4, obtained in Example 1, was placed in the glass closed container of Example 1.
4'-bis (3-nitrophenoxy) biphenyl 100
g (0.23 mol) 5% pd / c (Nippon Engelhard Co., Ltd.)
Charge with 1 g, 350 ml methyl cellosolve. 6
When hydrogen was introduced with vigorous stirring at 0 to 65 ° C., it was not absorbed any more in 8 hours, and the reaction was completed.

Post-treatment and purification were carried out in the same manner as in Example 1,
4,4'-bis (3-aminophenoxy) biphenyl was obtained. Yield 70.3 g (yield 83%) Colorless crystals mp. 144-146 ° C Purity 99.3% (by high performance liquid chromatography) Reference Example-1 In a container equipped with a stirrer, a reflux condenser and a nitrogen inlet tube, 4,4 36.8 g (0.1 mol) of ′ -bis (3-aminophenoxy) biphenyl and 175.8 g of N, N-dimethylacetamide were charged, and 21.8 g (0.1 mol) of pyromellitic dianhydride under a nitrogen atmosphere at room temperature. Was added in portions while paying attention to the rise in solution temperature, and the mixture was stirred at room temperature for about 20 hours. The polyamic acid thus obtained has an inherent viscosity of 2.47 dl.
/ G. After taking a part of this polyamic acid solution and casting it on a glass plate, 100 ° C., 200 ° C., 30
Heated at 0 ℃ for 1 hour each, transparent with light yellow color, film thickness 35
A polyimide film of μ was obtained. The polyimide film had a tensile strength of 14.8 kg / mm ² and a tensile elongation of 70%. (The measuring method is based on ASTM D-882.
The same applies below. ) Further, the glass transition temperature of this polyimide film is 271 ° C. (measured by the TMA penetration method.
The 5% weight loss temperature in air was 545 ° C. (measured with DTA-TG. The same applies hereinafter). Furthermore, this polyimide film was preheated to 130 ° C, which was a cold rolled steel plate (JIS G3
141, spcc / SD, 25 × 100 × 1.6mm. The same applies below. )
It was inserted between them and pressure-bonded at 340 ° C. and 20 kg / cm ² for 5 minutes. The tensile shear bond strength of this product at room temperature is 31
It was 0 kg / cm ² , and when it was further measured at a high temperature of 240 ° C., it was 205 kg / cm ² . (Measurement method is JIS
-Based on K6848 and 6850. The same applies below. The water absorption of this film when immersed in water at 23.5 ° C. for 24 hours was 0.52%. (Measurement method is ASTM D-57
According to 0-63. ) Also, the above polyamic acid solution is applied onto a cold-rolled steel sheet that has been washed with trichloroethylene,
After heating and drying at 1 ° C. for 1 hour and 220 ° C. for 1 hour, cold-rolled steel sheets were stacked and pressure-bonded at 300 ° C. to 20 kg / cm ² for 5 minutes. The tensile shear bond strength of this product is 280 at room temperature.
It was kg / cm ² .

Further, the above polyamic acid solution was cast on an electrolytic copper foil and then heated at 100 ° C., 200 ° C. and 350 ° C. for 1 hour to obtain a flexible copper clad circuit board. The thickness of the coating film was about 35μ. The copper foil peeling strength of this copper-clad circuit board was 2.8 kg / cm in the 90 ° peel strength test. Moreover, even when immersed in a solder bath at 300 ° C. for 180 seconds, no blistering or the like occurred.

Also, 337.5 g of N, N-dimethylacetamide was added to 150 g of the above polyamic acid solution, and the mixture was heated to 70 ° C. under stirring in a nitrogen atmosphere and then 26.1 g (0.26 mol) of acetic anhydride and 9.05 g (0.09 mol) of triethylamine. When, was added dropwise, yellow polyimide powder began to precipitate in about 10 minutes after the completion of the addition, but the mixture was further stirred under heating for 2 hours and then hot filtered to obtain a polyimide powder. This polyimide powder was washed with methanol and dried under reduced pressure at 150 ° C. for 5 hours to obtain 34.5 g (yield 98%) of polyimide powder.
An X-ray analysis of this polyimide powder showed that it had a crystallinity of 21%.

The infrared absorption spectrum of this polyimide powder is shown in FIG. This spectrum diagram, around 1780 cm ^-1 and near 1720 cm ^-1 which is the characteristic absorption band of imide, and absorption at around 1240 cm ^-1 which is the characteristic absorption band of ether linkage was clearly observed.

The glass transition temperature and melting point of this polyimide powder were 260 ° C and 367 ° C, respectively. (Measured by DSC method) Further, the notched Izod strength of the compression molded product obtained by compression molding this polyimide powder at 400 ° C. and 300 kg / cm ² for 30 minutes was 18 kg · cm / cm. (Measurement method is ASTM D-25
According to 6. Reference Example-2 In Reference Example-1, 4,4'-bis (4-aminophenoxy) biphenyl was used instead of 4,4'-bis (3-aminophenoxy) biphenyl, and Reference Example-1 was used. The same operation was performed to obtain a polyamic acid solution having an inherent viscosity of 1.50 dl / g. Using this polyamic acid, a polyimide film and a polyimide powder were obtained in the same manner as in Reference Example-1.

The 5% weight loss temperature of this polyimide film in air was 533 ° C. Further, using this film, a cold-rolled steel plate was pressure-bonded in the same manner as in Reference Example-1. The tensile shear adhesive strength of this product at room temperature was 50 kg / cm ² .

Moreover, this polyimide powder did not have a glass transition temperature and did not show a fluidized state even when the temperature was raised.

[Brief description of drawings]

FIG. 1 is an infrared absorption spectrum diagram of the polyimide powder obtained in Reference Example-1.

Claims (1)

[Claims] 1. A formula (1) 4,4'-bis (3-aminophenoxy) represented by
Biphenyl