JPS6270347A - 4,4'-bis(3-aminophenoxy)biphenyl - Google Patents

Abstract

NEW MATERIAL:4,4'-Bis(3-aminophenoxy)biphenyl expressed by the formula. USE:A raw material for polymide resins, having excellent improved processability and heat-resistance adhesive property in addition to improved heat resistance essential to the polymide resins, low water absorption, good transparency and useful as a raw material for multipurpose resins. PREPARATION:4,4'-Dihydroxybiphenyl is reacted with m-nitrobenzene in the presence of a base, e.g. potassium carbonate, in an aprotic polar solvent, e.g. N,N-dimethylformamide, at 100-240 deg.C to afford the 4,4'-bis(3-nitrophenoxy) biphenyl, which is then reduced by catalytic reduction or hydrazine reduction, etc., to give the aimed compound expressed by the formula.

Description

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

(Prior art) Polyimide obtained by the reaction of tetracarboxylic dianhydride and diamine has been known to have various excellent physical properties, especially good heat resistance, and will be widely used in fields where even higher heat resistance is required in the future. It is expected that

However, conventionally known polyimide resins.

Those with excellent heat resistance have poor processability, and those developed for the purpose of improving processability have various problems such as poor heat resistance and solvent resistance. For example, polyimide resin (Dup
(manufactured by ont, product name Kapton, Vespel)
does not have a clear glass transition temperature, and although it has excellent heat resistance, it has poor processability, and when used as a molding material, it cannot be processed without using methods such as sintering. In addition, in recent years, polyimide resins have been used as base materials for electrical and electronic components due to their heat resistance and insulating properties. It has the disadvantage that it has a negative effect on dimensional stability, insulation properties, and soldering heat resistance, which are important factors when used as a material. In addition, polyetherimide resin (manufactured by GE, trade name: ULTEM) having a basic skeleton represented by formula (3) has excellent processability, but has a low glass transition temperature of 217°C. It has the disadvantage of poor heat resistance and is soluble in halogenated hydrocarbon solvents such as methylene chloride.

(Problems to be Solved by the Invention) An object of the present invention is to create a polyimide resin that has excellent processability and heat-resistant adhesion, low water absorption, and good transparency in addition to the excellent heat resistance that polyimide resin inherently has. The object of the present invention is to provide a novel compound, namely, aromatic ether diamine, which can be used as a raw material for polyimide resin that can be used for multiple purposes.

(Means for Solving the Problems) In order to achieve the above-mentioned problems, the present inventors have synthesized various diamines, manufactured polyimide resins using them as raw materials, and evaluated the performance thereof.

As a result, 4,4'-bis(3-aminophenoxy)biphenyl represented by the formula (1) was produced for the first time.

This compound has excellent heat resistance, processability, transparency, and low water absorption in a polymer with tetracarboxylic dianhydride, and this new aromatic ether diamine is preferable as a raw material for heat-resistant resin. I found out.

That is, one aspect of the present invention is 4,4'-bis(3-aminophenoxy)biphenyl, which is a novel aromatic ether diamide 7.

Conventionally, in aromatic nitro compounds, many examples are known regarding the reaction of substituting a nitro group of a compound activated by an electron-withdrawing group at the 0- or p-position with a phenol. However, for the reaction of unactivated nitro groups such as m-dinitrobenzene, 1m-dinitrobenzene and an alkali metal phenoxide are reacted in a polar organic solvent in the presence of a macrocyclic polyether. - Only a method for producing nitrodiphenyl ether is known (JP-A-54-39030).

Moreover, by condensing 4,4-dihydroxybiphenyl having two hydroxyl groups with two molecules of m-dinitrobenzene, aromatic ether diamines such as 4,4-bis(3-aminophenoxy)biphenyl can be produced. There is no known method for producing it, and of course the compound itself is not known at all.

The present inventors investigated the synthesis of heat-resistant resin.

When 4.4I-dihydroxybiphenyl and m-dinitrobenzene are reacted in an aprotic polar solvent in the presence of a base, 4.4'-bis(3-nitrophenoxy)biphenyl can be produced in good yield; By reducing this, 4,4'-bis(3-aminophenoxy)biphenyl was successfully synthesized. Next, a polymer was produced using this compound as a raw material, and it was confirmed that this polymer had extremely excellent performance. That is, this compound is
It was confirmed that the present invention has a high degree of usefulness, and the object of the present invention was achieved.

The raw materials used in the production of the compounds of the present invention are 4°4'-
They are dihydroxybiphenyl and m-dinitrobenzene, and the amount used is not particularly limited, but usually the molar amount of 1m-dinitrobenzene is 1.5 to 3 times that of 4°4'-dihydroxybiphenyl.

The condensation reaction between 4.4'-dihydroxybiphenyl and m-dini].lobenzene is carried out in an aprotic polar solvent in the presence of a base.

This condensation reaction yields 4,4'-bis(3-nitrophenoxy)biphenyl, which is then reduced to 4,
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 potassium carbonate, sodium carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate, etc. are usually used. Used a lot.

The amount of the base is usually 1 to 5 times the mole, preferably 1.5 to 3 times the mole of 4,4-dihydroxybiphenyl as the raw material.

During this reaction, quaternary ammonium salts, quaternary phosphorus salts, macrocyclic polyethers such as crown ether, nitrogen-containing macrocyclic polyethers such as cryptate, nitrogen-containing chain polyethers, polyethylene glycols and their alkyl ethers A phase transfer catalyst such as, copper powder, copper salt, etc. may be added as a reaction accelerator.

As the reaction solvent, an aprotic polar solvent is used. For example N,N-dimethylformamide.

N,N-dimethylamide, dimethylsulfoxide, 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 charging all the raw materials containing 1m-dinitrobenzene from the beginning and allowing the reaction to proceed as they are.

The reaction temperature is 100-240°C, preferably 120-1
The temperature is in the range of 80°C and the time for one reaction is in the range of 5 to 30 hours. After the reaction is complete, the desired crude product can be obtained by distilling off the solvent or by directly discharging the reaction solution into water. This crude product can be purified by recrystallization etc., but usually.

Continue the reduction reaction. There are no particular restrictions on the reduction reaction, and 1. Usually, 2.1.
New Experimental Chemistry Course, Volume 15, Oxidation and Reduction [■], Maruzen (1
977)) can be applied, but catalytic reduction or hydrazine reduction is preferred industrially.

Examples of catalytic reduction are nickel and palladium.

4,4'-bis(
Based on 3-nitrophenoxy)biphenyl, 0.01 to 10% by weight as metal, therefore 2 to 8% by weight when used in the metal state, and 0.1 to 5% by weight when supported on a carrier. The reduction reaction is carried out using a range of .

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

The reaction temperature is not particularly limited. Generally 20-200
A range of 0.degree. C., particularly 20 to ioO'c, is preferred. Moreover, one reaction pressure is usually about normal pressure to 50 kg/d-6.

On the other hand, to give an example of hydrazine reduction, hydrazine is reduced to 1
Usually, the reduction reaction is carried out using 1.2 to 2 times the theoretical amount.

As the catalyst, metal catalysts commonly used for catalytic reduction can be used. Particularly preferred are catalysts in which palladium/carbon, platinum/carbon or ferric chloride is adsorbed on activated carbon. The amount used is usually 4.4 of the raw material.
The metal content is in the range of 0.01 to 30% by weight based on '-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 the reaction is completed, the reaction solution is heated to remove the catalyst, and if necessary, the solvent is distilled off to obtain the desired crude product of 4゜4'-bis(3-aminoneenoxy)biphenyl. . This crude product can be purified by recrystallization or isolation as a 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 dianhydrides to obtain a polyamic acid, and this can be further cyclized and dehydrated to obtain a polyimide.

The resulting polymer has extremely excellent processability and heat-resistant adhesive properties.

Such performance is due to the fact that the polymer consisting of 4,4'' (4-aminophenoxy)biphenyl and biromelinate dianhydride, which has a different diamine substitution position from that of the compound of the present invention, does not have a clear glass transition temperature; It has a remarkable difference in effectiveness compared to the case where it exhibits no adhesive strength at all.

Similarly, 4'-bis(4-aminophenoxy)biphenyl does not have a clear glass transition temperature even if it is a polymer with benzophenone tetracarboxylic dianhydride, has poor adhesive strength, and is poor in processability.

A polymer having the repeating unit of the formula (2) using the compound of the present invention as a raw material, particularly polyimide, has heat resistance peculiar to conventional polyimide.

Because they are thermoplastic, they have excellent processability and heat-resistant adhesive properties, and some of them are polyimide resins that have high heat resistance and can be melt-molded. Furthermore, it has low water absorption, and when considered with the above-mentioned excellent processability, it can be used as a base material for space and aircraft.
Its usefulness is demonstrated widely as a base material for electrical and electronic parts, and furthermore as a heat-resistant adhesive.

(Actions and Effects) 4,4' which is a novel aromatic ether diamine of the present invention
-bis(3-aminophenoxy)biphenyl is 4.4
It can be easily produced industrially by condensation and reduction reaction of '-dihydroxybiphenyl and m-dinitrobenzene. Additionally, when this compound is polymerized with tetracarboxylic dianhydride, a new polymer is obtained, which 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 fields where further heat resistance is required in the future.

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

Example 1 3t! A glass reaction vessel was charged with 186 f (1.0 mol) of 4,4'-dihydroxybiphenyl, 438 g (2.6 mol) of m-dinitrobenzene, 363 g of potassium carbonate, and 2000 ml of N,N-dimethylformamide.
React at 45-150°C for 16 hours. After the reaction was completed, the KNO2 was removed by cooling and filtration, and the solvent of the P solution was distilled off under reduced pressure.
0- and stirred for 1 hour. The crystals were separated, washed with water, washed with methanol, and dried to obtain brown crystals of 4,4'-bis(3-nitrophenoxy)biphenyl. Yield 426f
(Yield 99.5%) Then, II! Crude 4.4'-His (
3-nitrophenoxy)biphenyl 100f(0,23
469 (0.92 mol) of hydrazine hydrate was added dropwise over 3 hours at 6° C. and 10 f of activated carbon. After the dropwise addition was completed, the reaction was completed by stirring at 70 to 80°C for 5 hours. After cooling.

Filter to remove the catalyst, drain it into 500ml of water and filter the crystals. 48 g of 35% hydrochloric acid and (3-aminophenoxy)biphenyl hydrochloride were precipitated. After filtering this, 50% IPA/water 540- was added and dissolved by heating.
After adding 5 f of activated carbon and filtering, the mixture was neutralized with aqueous ammonia, and the crystals were filtered, washed with water, and dried to obtain 4,4'-bis(3-aminophenoxy)biphenyl. Yield 72.0g (
Yield 85%) Colorless crystals mp, 144-b Purity 99.6% (by high performance liquid chromatography) CHN Elemental analysis Calculated value (%) *) 78.26 5.43
7.61 Analysis value (%) 78.56 5.21
7.66*) C24I (MS as 20N202: 368 (M”), 340,184IR (KBr,
cm-”): 3400 and 3310 (NH2 group),
1240 (ether bond) Example 2 The crude 4.4 obtained in Example 1 was placed in a sealed glass container of 11.
'-His(3-nitrophenoxy)biphenyl 100g
(0.23 mol) was charged together with 1 g of 5% PD/C (manufactured by Nippon Engelhard) and methyl cellosolve 350-. Hydrogen was introduced at 60-65° C. with vigorous stirring, and no further absorption occurred in 8 hours, completing the reaction.

Post-treatment and purification were carried out in the same manner as in Example 1, and 4
．． 4'-bis(3-aminophenogysi)biphenyl was obtained. Revenue! 70.3g (yield 83%) colorless crystals mp,
144-146°C Purity 99.3% (by high performance liquid chromatography) Reference example-1 4.4'-bis(3-ami!phenogisi)biphenyl was placed in a container equipped with a stirrer, a reflux condenser, and a nitrogen introduction tube. 36.8f (0.1 mol) and 175.8 g of N,N-dimethylacetamide were charged, and 21.89 (0.1 mol) of pyromellitic dianhydride was added at room temperature under a nitrogen atmosphere.
was added in portions, paying attention to the rise in solution temperature, and the mixture was stirred at room temperature for about 20 hours.

The logarithmic viscosity of the polyamic acid thus obtained was 2.47r.
tt, /9. A portion of this polyamic acid solution was taken and cast onto a glass plate, and then heated at 100°C and 20°C.
The mixture was heated at 0° C. and 300° C. for 1 hour each to obtain a pale yellow transparent polyimide film with a film thickness of 35/I. This polyimide fill! The tensile strength of , is 14.8kg/w
d. The tensile elongation rate was 70%. (Both measurement methods are based on ASTM 1)-882. (Same as above.)
In addition, the glass transition temperature of this polyimide film is 27
1℃ (Measured by TMA needleman method.Hereafter, the temperature of 5% weight loss in air was 545℃ (Measured by DTA-TG.The same applies hereafter.) A cold-rolled steel plate (JTS) with a polyimide film preheated to 130°C
G3141.5pcc/Sl).

25X100XI, 6 directions. Same below. ), insert between 3
Pressure bonding was carried out at 40'C and 20 kg/ci for 5 minutes. The tensile shear adhesive strength of this product at room temperature is 310 kg/c
J, and when this was further measured at a high temperature of 240°C, it was 205 kg/d. (Measurement method is J
One or more according to IS-K 6848 and 6850. ) Also, this film was heated at 23.5℃ for 24 hours.
The water absorption rate when immersed in water for an hour was 0.52%. (
The measurement method is based on ASTM I)-570-63. )
Further, the polyamic acid solution described in -1- was applied onto a cold rolled steel plate that had been washed with trichlorethylene, and the solution was heated at 100°C for 1 hour.

After heating and drying at 220°C for 1 hour, cold rolled steel plates were stacked and pressed at 300°C for 5 minutes at 20 kg/cd.

The tensile shear adhesive strength of this product is 280 kg/c at room temperature.
It was j.

Furthermore, the above polyamic acid solution was cast onto an electrolytic copper foil and heated at 100°C, 200°C, and 350°C for 1 hour each to obtain a flexible copper-clad circuit board.3 The thickness of the coating film was approximately 35μ. Ta. The copper foil peeling strength of this copper-clad circuit board is 2.8 ka in a 90° building strength test.
/c+I. Further, even when immersed in a solder bath at 300° C. for 180 seconds, no blistering occurred.

Further, 337.59 y of N,N-dimethylacetamide was added to 150 y of the above polyamic acid solution, and after heating to 70°C under a nitrogen atmosphere while stirring, 26.1 g (0.
, 26 mol) of acetic anhydride and 9.05f (0.09 mol) of triethylamine were added dropwise, and yellow polyimide powder began to precipitate approximately 10 minutes after the completion of one drop.
After further stirring under heating for 2 hours, the mixture was filtered under heat to obtain polyimide powder. 34. This polyimide powder was washed with methanol and then dried under reduced pressure at 150°C for 5 hours. ．． 59C yield 9
8%) polyimide powder was obtained. X-ray analysis of this polyimide powder revealed that it had a degree of crystallinity of 21%.

Furthermore, an infrared absorption spectrum diagram of this polyimide powder is shown in FIG. In this spectrum diagram, absorption near 1780G-'Iq and 1720♂1, which are the characteristic absorption bands of imide, and absorption near 12401', which is the characteristic absorption band of ether bonds, were clearly observed.

The polyimide powder had a glass transition temperature of 260°C and a melting point of 367°C. (1) Measured from S c Hoshin)
In addition, this polyimide powder was heated at 400℃ and 300 kg/CI.
The notched Izo strength of the compression molded product obtained by compression molding at l+2 for 30 minutes was 18 kg·Cm/CHl. (The measurement method is based on ASTM D-256.)

[Brief explanation of drawings]

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

Claims (1)

[Claims] 1) 4,4'-bis(3-aminophenoxy) represented by formula (1) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(1)
biphenyl