JPH0745445B2 - 4,4 '"-bis (3-aminophenoxy) -3,3"', 5,5 '"-tetramethylbiphenyl and process for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention provides 4,4′-bis (3-aminophenoxy) -3,
The present invention relates to 3 ', 5,5'-tetramethylbiphenyl and a method for producing the same.

More specifically, it is obtained by condensing 4,4'-dihydroxy-3,3 ', 5,5'-tetramethylbiphenyl and m-dinitrobenzene in the presence of a base in an aprotic polar solvent.
4,4'-bis (3-nitrophenoxy) -3,3 ', 5,5'-
Tetramethylbiphenyl obtained by further reduction 4,
It relates to 4'-bis (3-aminophenoxy) -3,3 ', 5,5'-tetramethylbiphenyl.

4,4′-bis (3-aminophenoxy) -3 of the present invention,
3 ', 5,5'-Tetramethylbiphenyl has never been prepared and therefore its known use is unknown.

However, due to its structure, a monomer of heat-resistant polymer,
In particular, it is useful as a basic raw material for polyamide, polyimide, polyamino bismaleide 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 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 (3) The polyimide resin consisting of the basic skeleton represented by (Dupont, trade name Kapton.Vespel) does not have a clear glass transition temperature and is excellent in heat resistance but inferior in processability and is used as a molding material. In this case, it cannot be processed unless a technique such as sintering is used.

Further, in recent years, a polyimide resin has been used as a base material for electric / electronic components because of its heat resistance and insulating properties. However, the polyimide resin represented by the formula (3) has high water absorption and is a material for electric / electronic components. 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, equation (4) Polyetherimide resin with a basic skeleton represented by (GE Company, trade name ULTEM) has excellent processability, but has a low glass transition temperature of 217 ° C, poor heat resistance, and halogen such as methylene chloride. It has a drawback that it is soluble in a compounded hydrocarbon solvent.

The present inventors have previously found that a polyimide resin containing 4,4′-bis (3-aminophenoxy) vinylifer as a diamine component has excellent heat resistance, processability, transparency, low water absorption and adhesiveness. Was filed and filed (Japanese Patent Application No. 60-21026
6).

(Problems to be Solved by the Invention) An object of the present invention is to provide a raw material of a polyimide resin which has excellent workability and heat-resistant adhesiveness, in addition to the excellent heat resistance originally possessed by the polyimide resin, and which can be used for multipurpose purposes. It is to provide a novel compound, namely an aromatic ether diamine.

(Means for Solving Problems) The present inventors have synthesized various diamines to achieve the above-mentioned problems, manufactured polyimide resins using them as raw materials, and evaluated their performance. As a result, 4,4'-bis (3-aminophenoxy) -3,3 ', 5,5'-tetramethylbiphenyl represented by the formula (1) was produced for the first time, and this compound was used as tetracarboxylic acid dianhydride. It has been found that the novel aromatic ether diamine has excellent heat resistance and processability as a polymer with a polymer and is preferable as a heat resistant resin raw material.

That is, the present invention is 4,4'-bis (3-aminophenoxy) -3,3 ', 5, which is a novel aromatic ether diamine.
It relates to 5'-tetramethylbiphenyl and a method for producing the same.

Conventionally, in an aromatic nitro compound, many examples are known regarding the reaction of substituting the nitro group of a compound activated by an 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). Furthermore, by condensing 4,4'-dihydroxy-3,3 ', 5,5'-tetramethylbiphenyl having two hydroxyl groups and two molecules of m-dinitrobenzene, 4,4'-bis ( There is no known method for producing an aromatic ether diamine such as 3-aminophenoxy) -3,3 ', 5,5'-biphenyl, and, of course, the compound itself has never been known.

The present inventors have investigated 4,4′-
When dihydroxy-3,3 ', 5,5'-tetramethylbiphenyl and m-dinitrobenzene are reacted in the presence of a base in an aprotic polar solvent, 4,4'-bis (3-nitrophenoxy)- 3,3 ', 5,5'-Tetramethylbiphenyl can be produced, and by further reducing it, 4,4'-bis (3-aminophenoxy) -3,3', 5,5'-tetramethylbiphenyl Was successfully synthesized. 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 method used to prepare the compounds of the present invention is 4,
4'-dihydroxy-3,3 ', 5,5'-tetramethylbiphenyl and m-dinitrobenzene condensation reaction (hereinafter referred to as the first step reaction) and reduction reaction (hereinafter referred to as the second step reaction) It consists of two reactions.

The raw material 4,4'-dihydroxy-3,3 ', 5,5'-tetramethylbiphenyl used in the first-step reaction can be easily produced by oxidation of 2,6-dimethylphenol (Japanese Patent Laid-Open No. 2000-242242).
53-65834 and Journal of Organic Chemistry (J. Org Chem.), 50, 3927 (1985)).

The amount of raw material used is not particularly limited, but usually,
m-dinitrobenzene is 4,4'-dihydroxy-3,3 ',
It is used so as to be 1.5 to 3 times mol with respect to 5,5'-tetramethylbiphenyl. 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. It

The amount of base is usually 4,4'-dihydroxy-3,3 ', starting material.
The amount is 1 to 5 times, preferably 1.5 to 3 times the mol of 5,5'-tetramethylbiphenyl.

During this reaction, quaternary ammonium salt, quaternary phosphorus salt, macrocyclic polyether such as crown ether, nitrogen-containing macrocyclic polyether such as cryptate, 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, dimethyl sulfone, sulfolane, 1-methyl-2-pyrrolidinone or
Something like 1,3-dimethyl-2-imidazolidinone is used. These solvents are usually 1 to 10 relative to the raw materials.
Used in weight times.

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 in the range of 100 to 240 ° C, preferably 120 to 180 ° 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 the target crude product. This crude product can be purified by recrystallization or the like, but normally, the second stage reduction reaction is carried out as it is.

The second step reaction is not particularly limited, and a method of reducing a nitro group to an amino group can be usually applied (for example, New Experimental Chemistry Lecture, Volume 15, Oxidation and Reduction [II], Maruzen (1977)). From the viewpoint, 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) -3, 0.01 to 10% by weight of metal based on 3 ', 5,5'-tetramethylbiphenyl, therefore 2 to 8% by weight when used in a metal state, and 0.1 to 5% by weight when loaded on a carrier. The reduction reaction is performed within the range of%.

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, the range of 20 to 200 ° C, particularly 20 to 100 ° C is preferable. Also, the reaction pressure is
Usually, the atmospheric pressure is 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 theoretical amount.

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 4,4 '
It is in the range of 0.01 to 30% by weight as a metal based on -bis (3-nitrophenoxy) -3,3 ', 5,5'-tetramethylbiphenyl.

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, preferably 40 to 100 ° C.

After completion of the reaction, the reaction solution is hot filtered to remove the catalyst, and then the solvent is distilled off if necessary to obtain the desired 4,4′-bis (3-aminophenoxy) -3,3 ′, 5,5 A crude product of'-tetramethylbiphenyl is obtained. 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.

Polyimide resin using the compound of the present invention as a raw material, while having heat resistance peculiar to conventional polyimide resins, since it is thermoplastic, it has excellent processability and heat-resistant adhesiveness,
Some of them are high heat resistant and melt moldable polyimide resins.

Therefore, 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) -3,3 ', 5,5'-tetramethylbiphenyl is 4,4'-dihydroxy-3,3', 5,
It can be industrially easily produced by condensation and reduction reaction of 5'-tetramethylbiphenyl and m-dinitrobenzene.
Further, when this compound is polymerized with tetracarboxylic acid dianhydride, a novel polymer is obtained, and this polymer has excellent heat resistance, processability and adhesive ability. That is,
INDUSTRIAL APPLICABILITY The compound of the present invention can be widely used as a resin raw material in the field where heat resistance is required further in the future.

(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 charged with 4,
4'-dihydroxy-3,3 ', 5,5'-tetramethylbiphenyl 48.4 g (0.2 mol), m-dinitrobenzene 80.6 g
(0.48 mol), potassium carbonate 66.2 g (0.48 mol), N, N-
Charge 750 ml of dimethylformamide, and add 7.5 at 140-147 ℃.
Stir for hours. After cooling, it was discharged into water, extracted with benzene, and the solvent was concentrated under reduced pressure to give 4,4'-bis (3-nitrophenoxy) -3,3 ', 5,5'-tetramethylbiphenyl tan crystals. Got Yield 43.6g (yield 45.0%). The analytical sample was obtained by recrystallization from chloroform / ethanol.

m.p 186.6-187.5 ° C (corr) Yellow cubic IR (KBr.cm ^-1 ): 1530 and 1350 (NO ₂ group), 1225 (ether bond) Elemental analysis value (C ₂₈ H ₂₄ N ₂ O ₆ ) CHN calculated value (%) 69.41 4.99 5.78 Measured value (%) 69.68 4.99 5.77 4,4'-bis (3-nitrophenoxy) -3,3 ', 5,5'-tetra obtained in this way Methylbiphenyl 43.6g
(0.09 mol), iron (III) chloride hexahydrate 90 mg, activated carbon (ADP charcoal, manufactured by Toyo Calgon) 1.31 g, 2-methoxyethanol 200 ml are charged into a reaction flask and stirred at 80 to 90 ° C for 30 minutes. After that, 80% hydrazine hydrate 37.6 g (0.6 mol) was added to 80%.
The mixture is added dropwise at ~ 90 ° C over 3 hours and further stirred at 105 ° C for 1 hour. After cooling, filtration and washing were performed, and the solvent was concentrated under reduced pressure to obtain yellowish brown crystals. To this, a mixed solvent of 2-methoxyethanol and water was added, concentrated hydrochloric acid was added, and the mixture was heated and dissolved, treated with activated carbon, and then cooled and crystallized to obtain crystals of a hydrochloride. After neutralizing in water with aqueous ammonia, recrystallize with toluene to obtain the target 4,
4'-Bis (3-aminophenoxy) -3,3 ', 5,5'-tetramethylbiphenyl was obtained as white crystals.

Yield 29.7g (Yield 77.8%) mp 191.8-192.6 ° C (corr) IR (KBr.cm ^-1 ): 3475 and 3380 (NH ₂ group), 1200 (ether bond) Elemental analysis value (C ₂₈ H ₂₈ N ₂ O ₂ ) C H N calculated value (%) 79.21 6.65 6.60 Measured value (%) 79.14 6.61 6.53 Example 2 The same as Example 1 except that 1,3-dimethyl-2-imidazolidinone was used as the solvent. Reaction at 160 ° C for 5 hours to give 4,4'-bis (3-nitrophenoxy)
-3,3 ', 5,5'-Tetramethylbiphenyl was obtained. Yield 3
6.0 g (yield 37.2%) 4,4′-bis (3-nitrophenoxy) -3,3 ′, 5,5′-tetramethylbiphenyl thus obtained 29.8 g
(0.05 mol) was dissolved in 100 ml of 2-methoxyethanol, and 1 g of 5% Pd / C (manufactured by Nippon Engelhard Co., Ltd.) was added. When hydrogen is introduced with vigorous stirring at 45-50 ° C, 6
No more absorption in time and the reaction was complete.

Post-treatment and purification were carried out in the same manner as in Example 1 to obtain 4,4 ′.
-Bis (3-aminophenoxy) -3,3 ', 5,5'-tetramethylbiphenyl was obtained.

Yield 13.8 g (yield 65.0%) mp 191.8 to 192.6 ° C. (corr) Reference Example 1 In a container equipped with a stirrer, a reflux condenser and a nitrogen introducing pipe,
4,4'-bis (3-aminophenoxy) -3,3 ', 5,5'-
Charge tetramethylbiphenyl 7.0 g (0.0165 mol) and N, N-dimethylacetamide 42.4 g, and at room temperature under a nitrogen atmosphere, pay attention to the rise of the solution temperature of 3.6 g (0.0165 mol) of pyromellitic dianhydride. While dividing and adding, about 20 at room temperature
Stir for hours.

The polyamic acid thus obtained had an inherent viscosity of 1.16.
It was dl / g. A part of this polyamic acid solution was taken, cast on a glass plate, and then heated at 100 ° C., 200 ° C., and 300 ° C. for 1 hour each to obtain a pale yellow transparent polyimide film having a film thickness of 35 μ.

The tensile strength of this polyimide film was 10.76 Kg / mm ² , and the tensile elongation was 8.3%.
-882. The same applies below).

The glass transition temperature of this polyimide film is 324.
C. (measured by TMA penetration method, the same applies below), and the 5% weight loss temperature in air was 474.degree. C. (measured with DTA-TG. The same applies below). Furthermore, this polyimide film was preheated to 130 ℃ cold rolled steel plate (JIS G3141, spcc / SD, 25 × 100 × 1.
6 mm. The same applies to the following), and pressure-bonded at 350 ° C. and 20 kg / cm ² for 5 minutes. The tensile shear bond strength of this product at room temperature was 250 Kg / cm ² .

Reference Example 2 In a container equipped with a stirrer, a reflux condenser and a nitrogen introducing pipe,
4,4'-bis (3-aminophenoxy) -3,3 ', 5,5'-
Tetramethylbiphenyl 6.2 g (0.0146 mol) and N, N-dimethylacetamide 43.6 g were charged, and benzophenone tetracarboxylic acid dianhydride 4.7 g was added at room temperature under a nitrogen atmosphere.
(0.0146 mol) was added in portions while paying attention to increase in temperature, and the mixture was stirred at room temperature for about 20 hours.

The polyamic acid thus obtained had an inherent viscosity of 0.93.
It was dl / g. A part of this polyamic acid solution was taken, cast on a glass plate, and then heated at 100 ° C., 200 ° C., and 300 ° C. for 1 hour each to obtain a pale yellow transparent polyimide film having a film thickness of 35 μ.

The tensile strength of this polyimide film is 10.96 Kg / mm ² ,
The tensile elongation was 6.3%. The glass transition temperature of this polyimide film was 276 ° C, and the 5% weight loss temperature in air was 473 ° C. Further, this polyimide film was inserted between cold-rolled steel plates preheated to 130 ° C., and pressure-bonded at 350 ° C. for 20 minutes at 20 kg / cm ² .

The tensile and shear bond strength of this product at room temperature is 275 Kg / cm ²
Met.

Claims (2)

[Claims] 1. A formula (1) 4,4'-bis (3-aminophenoxy)-
3,3 ', 5,5'-Tetramethylbiphenyl. 2. Condensation of 4,4'-dihydroxy-3,3 ', 5,5'-tetramethylbiphenyl and m-dinitrobenzene in the presence of a base in an aprotic polar solvent to give a compound of formula ( 2) 4,4'-bis (3-nitrophenoxy)-
Formula (1) characterized in that 3,3 ′, 5,5′-tetramethylbiphenyl is prepared and further reduced 4,4'-bis (3-aminophenoxy)-
Method for producing 3,3 ′, 5,5′-tetramethylbiphenyl