JPH06730B2 - 6,6'-Bis (4-aminophenoxy) -3,3,3, '3'-tetramethyl-1,1'-spirobiindane and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial field of application) The present invention provides 6,6′-bis (4-aminophenoxy) -3,3,
The present invention relates to 3 ', 3'-tetramethyl-1,1'-spirobiindane and a method for producing the same.

(Technical Background of the Invention) This 6,6′-bis (4-aminophenoxy) -3,3,3 ′,
3'-tetramethyl-1,1'-spirobiindane (hereinafter,
(abbreviated as p-BASI) has never been produced before, and its use is unknown.

The present inventors newly produced this compound and found that it is useful as a raw material for a polyimide resin.

That is, while the conventional polyimide resin has high performance,
There was a drawback that the molding process was difficult.

For example, the most typical aromatic polyimide consisting of 4,4'-diaminodiphenyl ether and pyromellitic dianhydride (Dupont, trade name "Vespel") is insoluble and infusible, so it is special The method is used.

With this method, since a processed product having a complicated shape cannot be obtained, it has to be further processed by cutting or the like, resulting in an increase in cost and difficulty in molding, which is a major drawback.

Further, conventionally, the diamine having an indane structure is 5
-Amino-1- (4'-aminophenyl) -1,3,3
-Trimethylindane and 6-amino-1- (4'-
Aminophenyl) -1,3,3-trimethylindane is known. A polyimide resin composed of 3,3 ′, 4,4′-benzophenonetetracarboxylic acid anhydride and pyromellitic acid anhydride (trade name “XU-21” manufactured by Ciba-Geigy Co., Ltd.) is prepared by using the mixture of the above two kinds of diamines.
8 ") is manufactured. However, since the glass transition temperatures (Tg) are 320 ° C. and 400 ° C. or higher, respectively, it has excellent heat resistance, but on the other hand, it is expected that the molding process is difficult (coating
Plastic Pre-Prints (Coating & Plastics Preprin
ts), 35 (2) 77-82 (1975)).

(Problems to be Solved by the Invention) However, although the indane structure has an aliphatic carbon skeleton, it has excellent heat resistance and long-term thermal stability because it has no benzylic protons that are susceptible to oxidation at high temperatures. There is. The object of the present invention is to pay attention to such an indane structure, and if an aromatic ether bond is introduced into a diamine monomer in order to obtain flexibility with a more stable spirobiidan structure, a polyimide having excellent heat resistance and molding processability. It was expected that a resin could be produced.

The present invention provides a diamine monomer having such characteristics and a method for producing the same.

(Means for Solving the Problems) The inventors of the present invention have made extensive studies to achieve this object, newly synthesized p-BASI represented by the formula (1), and used this p-BASI. We have found that the polyimide resin has the expected performance.

For example, a polyimide resin composed of p-BASI and benzophenone tetracarboxylic acid dianhydride has a relatively low glass transition temperature of 265 ° C., a heat resistance of 5% weight loss in air of 500 ° C. or more, and a moldability, An extremely useful polyimide resin having excellent thermal stability was obtained.

That is, the present invention provides p-BASI which is a raw material of useful polyimide resin and 6,6'-dihydroxy-3,
Condensation and reduction of 3,3 ', 3'-tetramethyl-1,1'-spirobiindane and 4-chloronitrobenzene as raw materials
It has been completed by finding that the process can be performed in high yield.

Conventionally, 4-chloronitrobenzene and bisphenols are reacted to obtain a bis (4-nitrophenoxy) compound,
An example is known in which this is reduced to produce a bis (4-aminophenoxy) compound. For example, bis (4-nitrophenoxy) biphenyl is obtained from 4-chloronitrobenzene and 4,4'-biphenol and is reduced to produce bis4-aminophenoxy) biphenyl (28th National Sampe Symposium N
ational SAMPE Symposium), April issue, 12-14, 72
8 to 739 (1983)), bis (4-aminophenoxy) phenylpropane is produced from 2,2′-bis (4-hydroxyphenyl) propane (Rocz Chem 48 1459 (1).
974)).

However, an example of deriving p-BASI represented by the formula (1) from 6,6′-dihydroxy-3,3,3 ′, 3′-tetramethyl-1,1′-spirobiindane represented by the formula (2) Is not known.

The compounds of the present invention are 4-chloronitrobenzene and 6,6'-
It is produced from dihydroxy-3,3,3 ', 3'-tetramethyl-1,1'-spirobiindane as a raw material by a method comprising two steps of a condensation step and a reduction step.

First, in the condensation process, 4-chloronitrobenzene as a raw material and 6,6′-dihydroxy-3,3,3 ′, 3 ′ represented by the formula (2) are used.
-Tetramethyl-1,1'-spirobiindane in the presence of a base, using a solvent to react, represented by the formula (3) 6,
6'-Bis (4-nitrophenoxy), 3,3,3 ', 3'-tetramethyl-1,1'-spirobiindane is obtained. The raw material used in this condensation step is 6,6'-dihydroxy-3,3,
3 ', 3'-Tetramethyl-1,1'-spirobiindane can be produced by heat treating 2,2-bis (4-hydroxyphenyl) propane with sulfuric acid or concentrated hydrochloric acid (US Pat. No. 3,271,463).

The reaction is carried out using 2-chloronitrobenzene in a 2- to 3-fold molar quantity with respect to the bisphenol of the formula (2). It is preferably in the range of 2.1 to 2.4 times by mole. Examples of the base include alkali metal carbonates, hydrogen carbonates, hydroxides and alkoxides, such as potassium carbonate, sodium carbonate, potassium hydrogen carbonate, potassium hydroxide, sodium hydroxide, lithium hydroxide, sodium methoxide and potassium. Examples include isopropoxide and the like.

Among these, potassium carbonate, sodium hydroxide and potassium hydroxide are preferably used industrially. The amount of this base used is 6,6'-dihydroxy-3,3, the starting material.
It is 2 equivalents or more, preferably 2.2-3 equivalents, relative to 3 ', 3'-tetramethyl-1,1'-spirobiindane.

As the solvent used in the condensation process, a usual aprotic polar solvent is used. They are, for example, dimethyl sulfoxide, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone, hexamethylphosphortriamide, sulfolane and the like. In addition, an organic solvent immiscible with water, for example, benzene, toluene, xylene, chlorobenzene, 1,2-dichloroethane, 1,1,2-trichloroethane, etc. is used to react in a heterogeneous system of the organic solvent layer and the water layer. You can also The amount of the solvent used in these homogeneous and heterogeneous systems is not particularly limited, but usually,
It is sufficient to use 1 to 15 times the weight of the raw material.

The reaction temperature is usually in the range of 70 to 20 ° C, preferably 80 to 180 ° C.

The end point of this reaction can be determined by thin layer chromatography or high performance liquid chromatography while observing the reduction of unreacted intermediates.

As a general embodiment of this condensation process, in a homogeneous reaction using an aprotic polar solvent, a predetermined amount of 6,6'-
Dihydroxy-3,3,3 ', 3'-tetramethyl-1,
After charging 1'-spirobiindane, a base and a solvent to form an alkali metal salt of bisphenol, 4-chloronitrobenzene is added and reacted, or all the raw materials containing 4-chloronitrobenzene are added at the same time and the mixture is allowed to rise. It may be either heated to react. Of course, the present invention is not limited to these and can be appropriately implemented by other modes. The post-treatment method after the reaction can be carried out by concentrating the solvent or directly adding it to water or the like to obtain the intermediate compound.

In the method of conducting the condensation in a heterogeneous system using an organic solvent immiscible with water, a general phase transfer catalyst such as quaternary ammonium salt, quaternary phosphonium salt or crown ether is used.
For example, triethylbenzyl ammonium chloride,
Trioctylmethylammonium chloride, tetrabutylammonium bromide, tetraphenylphosphonium chloride, trioctylethylphosphonium chloride, 18-crown-6-ether and the like are used. Industrially inexpensive quaternary ammonium salts are often used. The amount of this catalyst used is generally 0.1 to the raw material.
It is in the range of 30% by weight, preferably 1 to 10% by weight.
In this reaction, in order to accelerate the reaction, it is possible to raise the temperature and carry out under slightly pressurized conditions.

The post-treatment method after completion of the reaction is to remove the aqueous layer by liquid separation and then perform steam distillation to obtain an intermediate compound, or recover the solvent as it is to obtain an intermediate compound. Next, this intermediate compound is reduced to lead to a desired product. In this reduction step, a method of catalytic reduction or hydrazine reduction in a solvent in the presence of a reducing catalyst is often used. As the solvent, water, alcohols such as methanol, ethanol, isopropanol, isobutanol, methyl cellosolve, ethyl cellosolve, ethylene glycol, propylene glycol, diglyme, tetraglyme, dioxane, tetrahydrofuran, glycols, ethers are preferably used. And optionally hexane, cyclohexane, benzene, toluene, ethyl acetate, butyl acetate, cyclochloromethane, 1,2-dichloroethane,
Aliphatic hydrocarbons such as 1,1,2-trichloroethane,
Aromatic hydrocarbons, esters and halogenated hydrocarbons can also be used. These solvents may be used alone or in combination of two or more. The amount of the solvent used is not particularly limited, but usually 1 to 15 times the weight of the raw material is sufficient.

As the reduction catalyst, commonly used reduction catalysts such as palladium, platinum, rhodium, ruthenium, Raney nickel, copper, iron and the like can be used. Although these catalysts can be used in a metal state, they are usually used by supporting them on the surface of a simple substance such as carbon, barium sulfate, silica gel and alumina.

Industrially, palladium and platinum catalysts each supported on activated carbon, or Raney nickel catalysts are used.

Further, in the hydrazine reduction, a catalyst in which ferric chloride such as ferric chloride or ferric sulfate is adsorbed on activated carbon is also preferably used. The amount of these catalysts used is in the range of 0.01 to 30% by weight as a metal based on the raw material, and usually in the range of 0.05 to 5% by weight when used by being supported on a carrier.

The reaction temperature is generally in the range of 0 to 150 ° C., especially 1
The range of 0 to 100 ° C is preferable.

In the catalytic reduction method, the reaction pressure is usually 50
Any pressure of kg / cm ² or less may be used, and there is no inconvenience even if it is performed at normal pressure.

In a general embodiment of this reduction step, a solvent is added to the intermediate compound obtained in the condensation step to dissolve or suspend it, and then a catalyst used in the reduction reaction is added to carry out reduction. In the hydrazine reduction, hydrazine is added dropwise at a predetermined temperature and the temperature is kept above a certain level until the reaction is completed. The catalytic reduction is performed until the absorption of hydrogen gas is quantified or the absorption of hydrogen gas is stopped.

The progress of the reaction can be known by thin layer chromatography or high performance liquid chromatography. After completion of the reaction, in any case, the target p-BASI can be obtained by concentrating the solvent or diluting it with water or the like.

(Action and Effect) The present invention provides a novel method for producing a diamine monomer.

Since this diamine monomer has a stable spirobiindane structure and an ether bond in the molecule, the polyimide resin using this monomer has extremely good thermal stability and is a useful compound as a raw material for polyimide resins.

Further, the polyimide resin using this compound has a feature that it can be molded and processed, and therefore a high-performance polyimide resin can be supplied.

That is, the present invention is a compound useful as a raw material for a polyimide resin, and a high purity of this compound in a simple work process,
It provides a method that can be produced in high yield, and its industrial significance is great.

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

Example 1 A reactor was equipped with a stirrer, a thermometer and a reflux condenser.
67.1-dihydroxy-3,3,3 ', 3'-tetramethyl-1,1'-spirobiindane 77.1 g (0.25
Mole), 4-chloronitrobenzene 86.7 g (0.5
5 mol), anhydrous potassium carbonate 41.4 g (0.3 mol)
Then, 350 ml of N, N-dimethylformamide was charged, and the reaction was carried out under stirring while nitrogen gas was passed through. The reaction was carried out at a temperature of 150 to 153 ° C for 8 hours to complete the reaction.

After the reaction was completed, the reaction mixture was diluted with 350 ml of water, and a pale yellow precipitate was deposited. The precipitate was filtered, washed with isopropanol and water, and dried. This is 6,6'-bis (4-
Nitrophenoxy) -3,3,3 ', 3'-tetramethyl-1,1'-spirobiindane, yield 13
It was 3.5 g (yield 97%).

This was recrystallized from methyl cellosolve to give pure white needle-like 6,6'-bis (4-nitrophenoxy) -3,3,3.
3 ', 3'-Tetramethyl-1,1'-spirobiindane was obtained. The melting point is 200.5 to 201.5 ° C, and the results of elemental analysis are as follows.

Then, the above 6,6'-bis (4-nitrophenoxy) -3,3,3,3 was added to a closed reduction reactor equipped with a stirrer and a thermometer.
3 ', 3'-Tetramethyl-1,1'-spirobiindane 11g (0.02mol), 5% Pd / C catalyst 0.3g
Then, 40 ml of methyl cellosolve was charged, and hydrogen gas was introduced with vigorous stirring.

When the reaction temperature was 70 to 80 ° C. for 8 hours, 2650
After absorbing ml of hydrogen and no more absorption was observed, the reaction was terminated. After completion of the reaction, the reaction mixture was heated to remove the catalyst and cooled to precipitate crystals. This was filtered, washed with isopropanol and dried. The obtained white flaky crystals were 6,6'-bis (4-aminophenoxy) -3,
It was 3,3 ', 3'-tetramethyl-1,1'-spirobiindane, the yield was 8.5 g (yield 86.6%), and the melting point was 214 to 215 ° C.

The results of elemental analysis and MS spectrum are as follows.

MS spectrum (M / e) M ⁺ 490,475,238,65 Example 2 6,6'-Dihydroxy-3,3,3 in a reactor equipped with stirrer, thermometer, reflux condenser and water separator. ', 3'
-Tetramethyl-1,1'-spirobiindane 77.1
g (0.25 mol), 96% flake caustic soda 2
2.9 g (0.55 mol), 30 ml of benzene and 250 ml of dimethylsulfoxide were charged, and the temperature was raised while nitrogen gas was passed through to carry out azeotropic dehydration in the refluxed state of benzene. Then, 86.7 g of 4-chloronitrobenzene
(0.55 mol) was added, and the reaction was carried out at a temperature of 100 to 110 ° C. for 3 hours. After completion of the reaction, the powdery substance was discharged into 500 ml of water and the precipitated powdery substance was dried and dried to give 137 g of 6,6'-bis (4-nitrophenoxy) -3,3,3 ', 3'-tetramethyl-1, 1'-spirobiindane was obtained (yield 99.5%).

Then, 6,6'-bis (4-nitrophenoxy) obtained in a reactor equipped with a stirrer, a thermometer and a reflux condenser.
-3,3,3 ', 3'-Tetramethyl-1,1'-spirobiindane 13.8 g (0.025 mol), ferric chloride 0.1 g, activated carbon 1.5 g and methyl cellosolve 3
0 ml was charged, and 5 g (0.1 mol) of hydrazine hydrate was added dropwise at a temperature of 100 to 105 ° C over 1 hour. After the dropping was completed, the reaction was continued for 4 hours at the same temperature to complete the reaction. After the completion of the reaction, the catalyst was removed and the post-treatment was carried out in the same manner as in Example 1 to obtain 11.0 g of p-BASI (yield 8
9.6%). The melting point was 214-215 ° C.

Example 3 In an autoclave equipped with a stirrer and a thermometer, 6,6'-
Dihydroxy-3,3,3 ', 3'-tetramethyl-
1,1'-spirobiindane 15.4 g (0.05 mol), 96% potassium caustic 6.2 g (0.105 mol), 4-chloronitrobenzene 17.3 g (0.11)
Mol), 50 ml of water, 100 ml of toluene and 1 g of trioctylmethylammonium chloride as a catalyst were charged and the reaction was carried out at a temperature of 130 to 140 ° C. for 12 hours. After completion of the reaction, the lower layer was extracted and the organic layer was distilled by steam to recover the solvent. After cooling, obtain the residue by passing over 100 ml
Recrystallized from methyl cellosolve of 21.5 g of 6,
6'-bis (4-nitrophenoxy) -3,3,3 ',
3'-Tetramethyl-1,1'-spirobiindane was obtained (yield 78.1%). Melting point is generally 199.5-20
It was 1.5 ° C.

11 g of this nitro compound was charged into a reduction reactor together with 0.2 g of 5% Pt / C contact and 100 ml of ethanol, and hydrogen was introduced with vigorous stirring for reduction. After completion of the reaction, remove excess contact and concentrate to a 15% aqueous hydrochloric acid solution 7
When 5 g was added dropwise, p-BASI hydrochloride was precipitated. This was washed with water, washed with water and neutralized with stirring in dilute ammonia water, whereby crystals of p-BASI, which was the target substance, were deposited. It was washed with water and dried to obtain 8.3 g (yield 84.6).
%).

Claims (2)

[Claims] 1. A formula (1) 6,6-bis (4-aminophenoxy) -3,3, represented by
3 ', 3'-Tetramethyl-1,1'-spirobiindane 2. 4-chloronitrobenzene and formula (2) By reacting 6,6'-dihydroxy-3,3,3 ', 3'-tetramethyl-1,1'-spirobiindane represented by the formula (3) 6,6'-bis (4-nitrophenoxy) -3,3, represented by
A formula characterized by producing 3 ', 3'-tetramethyl-1,1'-spirobiindane and further reducing it.
(1) 6,6′-bis (4-aminophenoxy) -3,3, represented by
Process for producing 3 ', 3'-tetramethyl-1,1'-spirobiindane.