JPH0737427B2 - 4,4'-bis [3- (4-aminophenoxy) benzoyl] diphenyl ether and method for producing the same - Google Patents

Description

TECHNICAL FIELD The present invention relates to 4,4′-bis [3- (4-aminophenoxy) benzoyl] diphenyl ether and a method for producing the same.

More specifically, 3- (4-nitrophenoxy) benzoic acid chloride and diphenyl ether are condensed into 4,4'-bis [3- (4-nitrophenoxy) benzoyl] diphenyl ether in the presence of a lulylic acid catalyst, and then condensed. To 4,4'-bis [3- (4-aminophenoxy) benzoyl] diphenyl ether obtained by reducing

4,4′-bis [3- (4-aminophenoxy) of the present invention
Benzoyl] diphenyl ether has never been produced and its use is unknown.

However, due to its structure, a monomer of heat-resistant polymer,
Particularly useful as a basic raw material for polyamide, polyimide and polyamino bismaleide resin, etc. [Prior Art] Conventionally, polyimides obtained by the reaction of tetracarboxylic dianhydride and diamine have various excellent physical properties, particularly good heat resistance. It is known that this is widely used in the field where heat resistance is required.

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 have various problems such as poor heat resistance and poor solvent resistance. Have a point. For example, formula (III) Polyimide having 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 when used as a molding material, it can be processed. Difficult and must be processed using techniques such as sintering.

Also formula (IV) Polyetherimide having a basic skeleton represented by (General Electric Co .; trade name ULTEM) is a resin with excellent processability, but has a low glass transition temperature of 217 ° C and halogenated methylene chloride. It is soluble in hydrocarbons and is not a satisfactory resin in terms of heat resistance and solvent resistance.

On the other hand, the formula (V) Polyether ether ketone having a basic skeleton represented by (ICI; trade name Victorex) has a glass transition temperature of 143 ° C, a melting point of 334 ° C, and a heat distortion temperature of 152 ° C.
It is inferior to conventional polyimides in terms of thermal properties.

[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 heat-resistant adhesiveness and can be used for multipurpose applications, that is, an aromatic ether diamine. Is to provide.

[Means for solving problems]

The present inventors have synthesized various diamines, manufactured polyimide resins using them as raw materials, and evaluated the performance thereof in order to achieve the above-mentioned problems. As a result, the formula (I) For the first time, 4,4'-bis [3- (4-aminophenoxy) benzoyl] diphenyl ether represented by
It has been found that this compound has excellent heat resistance, processability, and adhesiveness in a polymer with tetracarboxylic dianhydride, and that this novel aromatic ether diamine is preferable as a heat resistant resin raw material.

That is, the present invention is a novel aromatic ether diamine
The present invention relates to 4,4'-bis [3- (4-aminophenoxy) benzoyl] diphenyl ether and a method for producing the same.

The methods used to make the compounds of the present invention are 3-
Condensation reaction of (4-nitrophenoxy) benzoic acid chloride with diphenyl ether (hereinafter referred to as the first stage reaction)
And a reduction reaction (hereinafter referred to as the second stage reaction).

The starting material 3- (4-nitrophenoxy) benzoic acid chloride used in the first step reaction can be easily produced by condensing m-hydroxybenzoic acid and p-chloronitrobenzene and then chlorinating.

The amount of the raw material used is not particularly limited, but is usually 3- (4
-Nitrophenoxy) benzoic acid chloride is used in a 2-3 fold molar amount relative to the diphenyl ether.

As the catalyst used in this reaction, any Lewis acid catalyst used in a usual Friedel-Crafts reaction can be used.

As a catalyst usually used, anhydrous aluminum chloride,
Lewis acids such as anhydrous ferric chloride, anhydrous ferric sulfate, and boron trifluoride can be given.

The amount of these catalysts used is 1 to 2 mol in the case of anhydrous aluminum chloride with respect to 3- (4-nitrophenoxy) benzoic acid chloride, and anhydrous ferric chloride, anhydrous ferric sulfate, and trifluoride are required. Boron bromide and the like is 0.005-0.1 mol, preferably 0.01-0.05 mol.

The reaction does not require a solvent, but preferably a solvent is used. The solvent is not particularly limited, but an aliphatic halogenated hydrocarbon such as dichloromethane, chloroform, 1,2-dichloroethane, 1,1,2-trichloroethane, 1,1,2,2-tetrachloroethylene which is inert to the reaction. Besides, carbon disulfide and nitrobenzene are used.

The reaction temperature is not particularly limited, but is usually in the range of 0 to 200 ° C.

The end point of the reaction can be confirmed by quantifying the amount of hydrogen chloride gas generated or by means such as thin layer chromatography and high performance liquid chromatography.

After completion of the reaction, the reaction solution was discharged into water, and the solvent was distilled off if necessary to obtain a crude product of 4,4′-bis [3- (4-nitrophenoxy) benzoyl] diphenyl ether, which is usually , As it is, is used for the second reaction.

The second-stage reduction reaction is not particularly limited, and is usually a method of reducing a nitro group to an amino group (see, for example, New Experimental Chemistry Course,
Volume, oxidation and reduction [II], Maruzen (1977)) can be applied, but industrially catalytic reduction is preferred.

As an example of catalytic reduction, 4,4'-bis [3- (4- (4-
Nitrophenoxy) benzoyl] diphenyl ether is used in an amount of 0.01 to 10% by weight as a metal. Therefore, it is used in a range of 2 to 8% by weight when used in a metal state and 0.1 to 5% by weight when supported on a carrier. To be

The reaction solvent is not particularly limited as long as it is inert to the reaction, and examples thereof include alcohols such as methanol, ethanol and isopropyl alcohol, glycols such as ethylene glycol and propylene glycol, diethyl ether, dioxane, tetrahydrofuran and 2 -Ethanols such as methoxyethanol, esters such as ethyl acetate and butyl acetate, N, N-dimethylformamide, dimethyl sulfoxide and the like can be used.

The amount of the solvent used is sufficient to suspend or completely dissolve the raw materials, and is not particularly limited,
Usually, 0.5 to 10 times the weight of the raw material is sufficient.

The reaction temperature is not particularly limited. Generally, the range of 20 to 200 ° C, particularly 20 to 100 ° C is preferable. Also, the reaction pressure is
Usually, it is about normal pressure to about 50 kg / cm ² -G.

In the reaction, a catalyst is usually added in a state where raw materials are dissolved or suspended in a solvent, and then hydrogen is introduced at a predetermined temperature with stirring to carry out a reduction reaction. The end point of the reaction can be determined by the amount of absorbed hydrogen, thin layer chromatography, high performance liquid chromatography, or the like.

After completion of the reaction, the reaction solution is filtered to remove the catalyst and then cooled to obtain the desired aromatic ether diamine crystals.

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

[Action and effect]

The novel aromatic ether diamine of the present invention, 4,4'-
Bis (3- (4-aminophenoxy) benzoyl] diphenyl ether can be industrially easily produced by condensation and reduction reaction of 3- (4-nitrophenoxy) benzoic acid chloride with diphenyl ether.

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

The polyimide resin using the aromatic ether diamine of the present invention as a raw material is similar to the structure of the polyether ether ketone represented by the formula (V) in which an imide bond is introduced, and has a heat resistance higher than that of the polyether ether ketone. In terms of the above, there is a significant improvement, and the moldability is excellent.

That is, the polyimide resin using the compound of the present invention as a basic raw material, while having the same heat resistance as conventional polyimide, is excellent in processability and heat-resistant adhesiveness because it is thermoplastic, and among them Is a melt-moldable polyimide having high heat resistance. Furthermore, a polyimide film obtained from a certain tetracarboxylic dianhydride has an excellent feature that it is almost colorless.

Therefore, these polyimides are extremely useful polyimides as a space / aircraft base material, electric / electronic component base material, and as a heat-resistant adhesive.

That is, the compound of the present invention can be widely used as a resin raw material in a field in which further heat resistance is required in the future.

〔Example〕

Hereinafter, the present invention will be specifically described with reference to Examples and Reference Examples.

Example-1 In a two flask equipped with a stirrer, a reflux condenser and a thermometer, 309 g of 3-nitrophenoxybenzoyl chloride (1.
11 mol), diphenyl ether 85.5 g (0.502 mol), 1,
Charge 2-dichloroethane 1.

Under stirring, 198 g (1.49 mol) of anhydrous aluminum chloride are added portionwise over 1.5 hours so that the temperature does not exceed 40 ° C. Five
After stirring at 5-60 ° C. for a further 11 hours, cool and discharge into water 2.

The separated organic layer is washed with a 5% aqueous NaOH solution and the solvent is distilled off under reduced pressure to obtain a crude dinitro compound of the formula (II) as a tan oil. Yield 312 g (yield 95%) Part of this crude dinitro compound was separated by column chromatography using silica gel (Wako Pure Chemical Industries (C-100)) to obtain a purified dinitro compound as a yellow oil.

IR (neat, cm ^-1 ): 1650 (carbonyl group) 1340 (nitro group) 1230 (ether bond) This crude dinitro compound was added to 2-methoxyethanol 1.5
Into a catalytic reduction flask equipped with a reflux condenser, thermometer and stirrer, 16.5 g of 5% Pd / C is added.

When hydrogen is introduced at 30 to 35 ° C with vigorous stirring, absorption of hydrogen stops in 7.5 hours. The crystals obtained are filtered hot to remove P
When d / C is removed and cooled, pale yellow crystals are precipitated.

After filtration, washing, and drying, the desired aromatic diamine was obtained as pale yellow crystals.

Yield 253 (yield 85%) The crude crystals thus obtained were recrystallized from 2-methoxyethanol to obtain a pure product.

Light yellow scale crystal, mp169.5 ~ 171.5 ℃ (corr) Elemental analysis CHN calculated value (%) 77.01 4.76 4.73 Measured value (%) 76.86 4.59 4.65 IR (KBr disk, cm ^-1 ): 3380 (amino group) 1630 (Carbonyl group) 1220 (Ether bond) MS (FD method): 592 (M ⁺ ), 296 (M ⁺ / 2) Reference Example-1 A container equipped with a stirrer, reflux condenser and nitrogen inlet tube 23.71 g (0.04 mol) of 4'-bis [3- (4-aminophenoxy) benzoyl] diphenyl ether and N, N-
Dimethylacetamide (75.5 g) was charged, and pyromellitic dianhydride (8.64 g, 0.0396 mol) was dividedly charged at room temperature in a nitrogen atmosphere while being stirred, and stirred for 24 hours. The polyamic acid thus obtained has an inherent viscosity of 1.45 dl.
/ g (measurement temperature 35 ° C., N, N-dimethylacetamide solution, concentration 0.5 g / dl, and so on). After taking a part of this polyamic acid and casting it on a glass plate,
Heated at 00 ℃ and 300 ℃ for 1 hour each, light brown transparent and thickness 40μ
A polyimide film of was obtained. The glass transition temperature of this polyimide film is 230 ℃ (measured by TMA penetration method, the same applies below)
5% weight loss temperature in air is 545 ° C (measured with DTA-TG,
The same applies hereafter) Melting point: 387 ° C (measured by TMA penetration method, the same applies below)
Met. The tensile strength of this polyimide film is 1
It was 4.2 Kg / mm ² , and the tensile elongation was 13.3% (the same applies to the following measurement method according to ASTM D-882).

Reference Example-2 In a container equipped with a stirrer, a reflux condenser and a nitrogen inlet tube, 23.71 g (0.04 mol) of 4,4'-bis [3- (4-aminophenoxy) benzoyl] diphenyl ether and N, N-
Dimethylacetamide (74.9 g) was charged, and 8.38 g (0.0384 mol) of pyromellitic dianhydride was added in portions at room temperature in a nitrogen atmosphere while stirring while stirring the solution temperature, and the mixture was stirred for 24 hours.

The polyamic acid thus obtained had an inherent viscosity of 0.69 dl / g.
N, N-dimethylacetamide 214g was charged to the obtained polyimide acid solution, and the mixture was stirred under a nitrogen atmosphere,
12.25 g (0.12 mol) acetic anhydride and 10.15 g (0.
(15 mol) of triethylamine was added dropwise and the mixture was stirred for 24 hours.

The solution was discharged into water 1, the precipitate was filtered off, washed with methanol, and dried under reduced pressure at 150 ° C. for 8 hours to obtain 29 g of a pale yellow polyimide powder (yield 96.7%).

Glass transition temperature of this powder measured by DSC is 227 ° C, 5%
The thermal decomposition temperature was 540 ° C. According to the infrared absorption spectrum of the obtained polyimide powder here, 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 marked Was recognized by.

The melt viscosity was measured with a flow tester (CFT-500 manufactured by Shimadzu Corporation) using the powder obtained in this example. The orifice has a diameter of 0.1 cm, a length of 1 cm, and a load of 100 kg.

As a result, 5.2 × 10 ⁵ poise at 390 ° C and 8.2 × 10 ⁴ poi at 400 ° C
se, 1.2 × 10 ⁴ poise at 410 ° C, 8.5 × 10 ³ poise at 420 ° C, 43
It was 6.7 × 10 ³ poise at 0 ° C. The strands obtained at each temperature were brown, transparent and elastic.

Reference Example-3 23.71 g (0.04 mol) of 4,4'-bis [3- (4-aminophenoxy) benzoyl] diphenyl ether was added to a container equipped with a stirrer, a reflux condenser and a nitrogen inlet tube, and N, N.
-Charge 85.1 g of dimethylacetamide, and charge 12.76 g (0.0396 mol) of 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride in a nitrogen atmosphere at room temperature in portions while paying attention to the increase in melting temperature. Stir for 24 hours. The polyamic acid thus obtained had an inherent viscosity of 1.37 dl / g. After taking a part of this polyamic acid and casting it on a glass plate,
By heating at 100 ° C., 200 ° C. and 300 ° C. for 1 hour each, a light brown transparent polyimide film having a thickness of 40 μ was obtained. The glass transition temperature of this polyimide film was 200 ° C, and the 5% weight loss temperature in air was 531 ° C. The polyimide film had a tensile strength of 12.4 Kg / mm ² and a tensile elongation of 7.5%. Furthermore, this polyimide film was preheated to 130 ℃ and cold-rolled steel sheet (JIS G3141, SPCC / SD, 25mm × 100mmm
X 1.6 mm) and pressed at 320 ° C. for 50 minutes at 50 Kg / cm ² . The tensile shear bond strength of this product at room temperature is 303K.
It was g / cm ² , and when it was further measured at a high temperature of 240 ° C., it was 173 Kg / cm ² (the measuring method is according to JIS-K6848 and K-6850).

Further, the polyamic acid solution obtained in this example was applied to a cold-rolled steel sheet, dried and heated at 100 ° C. for 1 hour and 220 ° C. for 1 hour, and then stacked with another cold-rolled steel sheet at 320 ° C. 50 Kg / 5 in cm ²
Pressure was applied for a minute to perform pressure bonding. The thickness of the applied adhesive was 35μ. The tensile shear adhesive strength of this product is 310 Kg / at room temperature.
cm ² and measured at a high temperature of 240 ° C
It was 179 Kg / cm ² .

Further, the polyamic acid solution was cast on an electrolytic copper foil and then heated at 100 ° C., 200 ° C. and 300 ° 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 2.2 kg / cm in the 90 ° peel strength test. Also 300 ℃
No swelling occurred even when immersed in a solder bath for 60 seconds.

Claims (2)

[Claims] 1. A formula (I) 4,4'-bis [3- (4-aminophenoxy) benzoyl] diphenyl ether represented by 2. A compound of formula (II), which comprises condensing 3- (4-nitrophenoxy) benzoic acid chloride and diphenyl ether under a Lewis acid catalyst. A dinitro compound represented by the formula (I), which is characterized in that the dinitro compound is then reduced. For producing 4,4'-bis [3- (4-aminophenoxy) benzoyl] diphenyl ether represented by