JPS62108849A - 6,6-bis(4-aminophenoxy)-3,3,3',3'-tetramethyl-1,1'-spir obiindane and its production - Google Patents

Abstract

NEW MATERIAL:6,6'-Bis(4-aminophenoxy)-3,3,3',3'-tetramethyl-1,1'-spir obiindane of formula I. USE:A starting material of polyimide. A polyimide resin from the diamine of formula I and benzophenone tetracarboxylic dianhydride has a relatively low glass transition point of 265 deg.C, and over 500 deg.C at which the polymer looses its weight by 5% based on the original, thus having very good processability and high thermal resistance. PREPARATION:The reaction of 4-chloronitrobenzene with a compound of formula II in the presence of a base such as potassium carbonate gives a compound of formula III, then the product is reduced to give the objective compound of formula I. The reduction is carried out, e.g., catalytically in the presence of a catalyst in a solvent or by using hydrazine.

Description

Detailed Description of the Invention (Industrial Field of Application) The present invention relates to 6,6'-bis(4-aminophenoxy)-5
, 5,5',5'-tetramethyl-1,1'-spirobiindane and its production method.

(Technical background of the invention) This 6,6'-his(4-aminophenoxy)-5゜3
．． 3',3'-tetramethyl-1,1'-spirobiindane (hereinafter abbreviated as p-BASI) has never been produced, and its uses are unknown.

This compound was newly produced by the present inventors and found to be useful as a raw material for polyimide resin.

In other words, while polyimide resin has traditionally had high performance,
The drawback was that it was difficult to mold.

For example, the most typical aromatic polyimide consisting of 4,4'-diaminodiphenyl ether and pyromellitic anhydride (Pupont, trade name "Vespel J")
Because it is insoluble and infusible, a special method called powder sintering is used.

Since this method does not yield processed products with complex shapes, it must be further processed by cutting, etc., which increases costs and is a major drawback in addition to the fact that molding is difficult.

In addition, conventionally, as a diamine having an indane structure, 5
-amino-1-(4'-aminophenyl)-1,3,3
-trimethylindane and 6-amino-1-(4'-
(aminophenyl)-1,5,5-1-limethylindane is known. A polyimide resin (Ciba Geigy, trade name [XU
-218J) is manufactured.

However, the glass transition temperature (Tg) is 3
20℃, 400℃ or higher, it has excellent heat resistance, but on the other hand, it is expected that molding processing is difficult (coating Ik, Plastj, cs
Preprints), 35 (2) 77-82
(1975) ) 0 (Problem to be solved by the invention) However, although the inkun structure has an aliphatic carbon skeleton, it lacks heat resistance and long-term heat resistance because it does not have a Henzl position proton that is susceptible to oxidation at high temperatures. Excellent stability. The purpose of the present invention is to focus on such an indane structure, and to create a structure with excellent heat resistance and moldability by introducing an aromatic ether bond into a 7-amine monomer in order to obtain flexibility with a more stable spirohyndane structure. It was predicted that polyimide 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 present inventors made extensive studies to achieve this objective, synthesized a new p-BASI represented by the above formula (1), and used this p-BASI. It has been found that polyimide resin has the expected performance.

For example, a polyimide resin made of p-BASI and hensifhenonetetracarphonic dianhydride has a glass transition temperature that is significantly lower than 265°C, and its heat resistance is such that a 5% weight loss in air exceeds 500°C. An extremely useful polyimide resin with excellent moldability and thermal stability was obtained.

That is, the present invention provides p-BASI, which is a raw material for useful polyimide resins, and 6,6'-dihydroxy-
It was discovered and completed that it can be produced in high yield through two steps of condensation and reduction using 3,3,3',3'-tetramethyl-1,1'-spirobiindane and 4-chloronitrobenzene as raw materials. .

Conventionally, 4-chloronitrobenzene and bisphenols were reacted to obtain a bis(4-nitrophenoxy) compound,
An example of producing a bis(4-aminephenoxy) compound by reducing this is known.

For example, bis(4-nitrophenoxy)biphenyl is obtained from 4-chloronitrobenzene and 4,4'-biphenol, and bis(4-aminophenoxy)biphenyl is produced by reducing it. (National SAMPESymposi
um), April issue, 12-14, 728-739 (1
His(4-aminophenoxy)phenylpropane is produced from 2,2'-his(4-hyeroxinphenyl)propane (Rokutsuniki Chemie (983)).
Rocz Chem) 48 1459 (1974)
).

However, 6,6'-dihydroxy-3,3,3',3'-tetramethyl-1,1' represented by formula (2)
- p-BA represented by formula (1) from spirobiindan
There are no known cases of inducing SI.

The compounds of the present invention are 4-chloronitrobenzene and 6.6'
-Dihydroxy-5,3,3',3'-tetramethyl-1,1'-spirobiindane is used as a raw material and is produced by a method consisting of two steps: a condensation step and a reduction step.

First, in the condensation step, the raw material 4-chloronitrobenzene and 6,6'-dihydroxy-fila, 5
．． 3',3'-tetramethyl-1,1'-spirobiindane is reacted with a solvent in the presence of a base to form the formula (3
) 6,6'-bis(4-nitrophenoxy)-3,3,3';3'-tetramethyl-1,11-
Obtain Spirobindan. The raw material used in this condensation step, 6,6'-dihydroxy-5,3,3',3'-tetramethyl-1,1'-spirohiinc, is obtained by converting 2,2-bis(4-hydroquinphenyl)propane into sulfuric acid. Alternatively, it can be produced by heat treatment with concentrated hydrochloric acid (US Patent 3.
271,466).

The reaction is carried out using 2 to 5 times the mole of 4-chloronitrobenzene relative to the bisphenol of formula (2). Preferably, it may be in the range of 21 to 24 times the mole.

Bases 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, potassium Examples include isopropoxide.

Among these, potassium carbonate, sodium hydroxide, and potassium hydroxide are preferably used industrially. The amount of this base used is the raw material 6,6'-dihydroxy-3,
The amount is 2 or more equivalents, preferably 22-6 equivalents, relative to 3,3',3'-tetramethyl-1,1'-spirobiindane.

The solvent used in the condensation step is a common aprotic polar solvent. These are, for example, dimethylsulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, 1,6-dimethyl-2-imidazolidinone, hexamethylphosphortriamide, sulfolane and the like. Also, organic solvents that are immiscible with water, such as EVA, benzene, toluene, xylene, chlorobenzene, 1,2-dichloroethane, 1.1.2-
The reaction can also be carried out in a heterogeneous system of an organic solvent layer and an aqueous layer using trichloroethane or the like. The amount of solvent used in these homogeneous and heterogeneous systems is not particularly limited, but it is usually sufficient to use it in an amount of 1 to 15 times the weight of the raw material ζ.

The reaction temperature is usually in the range of 70 to 220'C,
Preferably it is in the range of 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.

A typical implementation of this condensation step is that in a homogeneous reaction using an aprotic polar solvent, a predetermined amount of 6,6'
-dihydroxy-ro, 3.5',5'-tetramethyl-
After charging 1,1'-spirobiindane, a base, and a solvent to form an alkali metal salt of bisphenol, 4-chloronitrobenzene is added and reacted, or all raw materials containing 4-chloronitrobenzene are added in advance at the same time. Alternatively, the reaction may be carried out by raising the temperature as it is.

Of course, the present invention is not limited to these examples, and can be implemented in other ways as appropriate. As for the post-treatment method after the completion of the reaction, the intermediate compound can be obtained by concentrating the solvent or pouring it directly into water or the like.

The method of carrying out the condensation in a heterogeneous system using an organic solvent that is immiscible with water uses a general phase transfer catalyst such as a quaternary ammonium salt, a quaternary phosphonium salt, or a crown ether.

For example, triethylbenzylammonium chloride,
Trioctylmethylammonium chloride, tetrabutylammonylam bromide, tetraphenylphosphonium chloride, trioctylethylphosphonium chloride, 18-crown-6-ether, etc. are used. Industrially, inexpensive quaternary ammonium salts are often used.

The amount of this catalyst used is usually in the range of 01 to 30% by weight, preferably 1 to 10% by weight based on the raw material. In order to speed up the reaction, this reaction can be carried out at elevated temperature and under slightly pressurized conditions.

As for the post-treatment method after the completion of the reaction, the aqueous layer is separated and removed, and then the intermediate compound is obtained by steam distillation, or the intermediate compound is obtained by directly recovering the solvent. next,
This intermediate compound is reduced to lead to the target compound. In this reduction step, a method using catalytic reduction or hydrazine reduction in the presence of a reduction catalyst in a solvent is preferably used. Examples of solvents include water, methanol, ethanol, impropatol, imbutanol, methyl cellosolve, ethyl Alcohols, glycols, and ethers such as cellosolve, ethylene glycol, propylene glycol, diglyme, tetraglyme, dioxane, and tetrahydrofuran are preferably used, and in some cases, hexane, cyclohexane, benzene, toluene, ethyl acetate, butyl acetate, and dichloromethane are used. , 1,2-dichloroethane, 1,
Aliphatic hydrocarbons such as 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 solvent to be 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, etc. can be used. Although these catalysts can be used in the form of metal, they are usually supported on the surface of a carrier such as carbon, barium sulfate, silica gel, alumina, or the like.

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

In the hydrazine reduction, activated carbon or the like adsorbed with a ferric salt such as ferric chloride or ferric sulfate is also preferably used as a catalyst. The amount of these catalysts used is in the range of 0.01 to 5° weight of metal based on the raw material,
Usually, when used as supported on a carrier, the amount is in the range of 0.05 to 5% by weight.

The reaction temperature is generally in the range 0 to 150'C, in particular,
A range of 10 to ioo°C is preferred.

In addition, in the catalytic reduction method, the reaction pressure is usually 50
Any pressure below kl/crd may be used, and there is no problem even if it is carried out at normal pressure.

In a typical 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 the reduction. In hydrazine reduction, hydrazine is added dropwise at a predetermined temperature, and the temperature is maintained above a certain level until the reaction is completed. Catalytic reduction is carried out until the absorption of hydrogen gas is determined quantitatively or until the absorption of hydrogen gas stops.

Progress of the reaction can be monitored by thin layer chromatography or high performance liquid chromatography. After the reaction is completed, in either case, the target product p-BASI can be obtained by concentrating the solvent or diluting it with water or the like.

(Functions and Effects) 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 its molecule, polyimide resins using this monomer have extremely good thermal stability, making it a useful compound as a raw material for polyimide resins.

Furthermore, a polyimide resin using this compound has the advantage of being moldable, and therefore a high-performance polyimide resin can be supplied.

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

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

Example 1 In a reactor equipped with a stirrer, a thermometer and a reflux condenser, 6
,6'-dihydroxy-5,5,5',5'-tetramethyl-1,1'-spirobiindane 77.1g (0,
25 mol), 4-chloronitrobenzene 86.7#
(0.55 mol), anhydrous potassium carbonate 41.1 (0.3
mol) and N,N-dimethylformamide 350 m/
! was charged, and the reaction was carried out under stirring while bubbling nitrogen gas. The reaction was completed at a temperature of 150-156°C for 8 hours.

After the reaction was completed, the mixture was diluted with 350 rnl of water, and a pale yellow precipitate was deposited. This precipitate was filtered, washed with impropatol and water, and then dried. This is 6.6′-bis(
The yield was 133.5.9 (97% yield).

This was recrystallized with methyl cellosolve to obtain white needle-like pure 6,6'-bis(4-nitrophenoxy)-3,5,3
',6'-tetramethyl-1,1'-spirobiindane was obtained. The melting point is 2005-2015°C, and the results of elemental analysis are as follows.

Calculated value (%1 72.0 5.49 5.
09 Next, the above 6,6'-bis(4-nitrophenoxy)-3,
11 g (0.02 mol) of 3,3',3'-tetramethyl-1,1'-spirobiindane, 5% Pd/C catalyst 0
．． 3 g and 40 ml of methyl cellosolve were charged, and hydrogen gas was introduced while stirring vigorously.

When the reaction temperature was 70-80℃ for 8 hours, the result was 2650
Hydrogen of at was absorbed, and since no further absorption was observed, the reaction was terminated. After the reaction was completed, the catalyst was removed by hot filtration and cooled to precipitate crystals. This was filtered, washed with impropatool, and then dried. The white scaly crystals obtained are 6,6'-bis(4-aminophenoxy) -
It was 5,5,5',3'-tetramethyl-1,1'-spirohiindane, and the yield was 85 g (yield 86.6%), and the melting point was 214-215°C.

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

CHN Calculated value (multi + 80.77 6.98 5
．． 71M5 spectrum (M/e) M+490,475,238.65 Example 2 6,6'-dihydroxy-filter, 3.3', 3'
-tetramethyl-1,1'-spirobiindane 77.1
g (0,25 mol), 96% flake caustic soda-22
, 9 g (0.55 moles), 30 ml of benzene, and 250 at of dimethyl sulfoxide were charged, and the temperature was raised while nitrogen gas was passed through the reactor to perform azeotropic dehydration of benzene under reflux. Then, 4-chloronitrobenzene 86.7
g (0.55 mol) was added thereto, and the reaction was carried out at a temperature of 100-110'C for 6 hours. After the reaction was completed, it was discharged into 500 atm of water, and the precipitated powder was filtered and dried to obtain 1371Q)6.
6'-bis(4-nitrophenoxy) -3,3,3'
.

6'-tetramethyl-1,1'-spirohiindane 14
(Yield: 995 cm).

The obtained 6,6′-bis(4-nitrophenoxy) was then placed in a reactor equipped with a stirrer, a thermometer and a reflux condenser.
-3,3,3',3'-tetramethyl-1,1'-spirobiindan 13.8.9 (0,025 mol), ferric chloride 0.1y, activated carbon 1.519 and methyl cellosolve 30ml. 5.9 (0.1 mol) of hydrazine hydrate was added dropwise over 1 hour at a temperature of 100 to 105°C. After the dropwise addition was completed, the reaction was continued at the same temperature for 4 hours to complete the reaction. After the reaction was completed, the catalyst was removed by filtration, and post-treated in the same manner as in Example 1 to obtain pBAsI 1109 (yield: 896). The melting point was 214-215°C.

Implementation ψl 3 6,6'- in an autoclave equipped with a stirrer and a thermometer.
Dihydroxo-3,3,5',3'-te-1-ramethyl-1,1'-spirobiincune 15.4 g (0.05 mol), 96% caustic potassium 6.2 g (0.105 mol),
4-chloronitrobenzea 17.3. ! i' (0
. After the reaction was completed, the lower layer was extracted and the organic layer was steam distilled to recover the solvent. After cooling, the residue was filtered and recrystallized with 100 ml of methyl cellosolve to give 2
15 g of 6,6'-his(4-nitrophenoxy) -
3,3,3',3'-tetramethyl-1,1'-spirobiindane was obtained (yield 781%). Melting point is 1995 ~
It was 20+, 5°C.

This 21-ro compound 11F was mixed with 0.2 g of 5% Pt/C catalyst and 100 m/! of ethanol! The mixture was charged into a reduction reactor, and hydrogen was introduced while vigorously stirring to perform reduction.

After the reaction was completed, the catalyst was removed by filtration, concentrated, and 75 g of 15-thihydrochloric acid aqueous solution was added dropwise to precipitate p-BASI hydrochloride. After filtering and washing with water, the mixture was stirred and neutralized in dilute ammonia water to precipitate the desired crystals of p-BA and SI. After filtration, washing with water, and drying, 8.31 was obtained (yield: 846%).

Claims (1)

[Claims] 1) 6,6'-bis(4-aminophenoxy) represented by formula (1) ▲There are mathematical formulas, chemical formulas, tables, etc.▼
-3,3,3',3'-tetramethyl-1,1'-spirobiindane 2) 4-chloronitrobenzene and formula (2) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(2) 6,6 represented by '-dihydroxy-3,3,3',
By reacting 3'-tetramethyl-1,1'-spirobiindane in the presence of a base, 6,6'-bis(4 -nitrophenoxy)
Formula (1) characterized by producing -3,3,3',3'-tetramethyl-1,1'-spirobiindane and further reducing it ▲There are mathematical formulas, chemical formulas, tables, etc.▼( 1) 6,6'-bis(4-aminophenoxy) represented by
- A method for producing 3,3,3',3'-tetramethyl-1,1'-spirobiindane.