JPH06728B2 - 1- [4- (3-aminophenoxy) phenyl] -1,3,3-trimethyl-6- (3-aminophenoxy) indane and method for producing the same - Google Patents

Description

TECHNICAL FIELD The present invention relates to 1- [4- (3-aminophenoxy) phenyl] -1,3,3-trimethyl-6- (3-aminophenoxy) indane and its production. Regarding the method.

(Technical Background of the Invention) This 1- [4- (3-aminophenoxy) phenyl]-
1,3,3-Trimethyl-6- (3-aminophenoxy) indane (hereinafter abbreviated as m-APAI) has never been produced 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 (Dupo) composed of 4,4-diaminodiphenyl ether and pyromellitic dianhydride.
nt company, trade name "Vespel") is insoluble and infusible, so a special method called powder sintering is used.

With this method, it is not possible to obtain processed products with complicated shapes.
Further, since it has to be processed by cutting or the like, the cost is increased and the molding is difficult, and there are major drawbacks.

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.

Using the above two kinds of diamine mixture,
A polyimide resin (trade name "XU-218", manufactured by Ciba-Geigy Co., Ltd.) composed of 3 ', 4,4'-benzophenone tetracarboxylic acid anhydride and pyromellitic acid anhydride is manufactured. However, since the glass transition temperatures (Tg) are 320 ° C. and 400 ° C. or higher, respectively, they have excellent heat resistance (coating, plastic, preprints (Coating & Plas).
ticsPreprints), 35 (2) 77-82
(1975)), however, it is expected that the molding process will be difficult.

However, the indane structure, despite having an aliphatic carbon skeleton, is excellent in heat resistance and long-term thermal stability because it has no benzylic protons that are susceptible to oxidation at high temperatures.

The present inventors have paid attention to the indane structure having such characteristics, and further diligently investigated the manufacturability of the m-position diamine introduced with an aromatic ether bond, and found the compound of the present invention.

The polyimide resin using this m-APAI is excellent in flexibility and moldability. That is, the polyimide resin composed of m-APAI and pyromellitic dianhydride has a relatively low glass transition temperature of 237 ° C., and has a heat resistance of 5% weight loss in air of 500 ° C. or more. An extremely useful polyimide resin having excellent properties was obtained.

(Prior Art) Conventionally, a method for producing this m-APAI has not been known.

The m-APAI of the present invention is a method of condensing m-dinitrobenzene and bisphenol having an indane ring to obtain a bis (3-nitrophenoxy) compound, and reducing this to produce.

Heretofore, in aromatic nitro compounds, many reactions have been known in which a nitro group activated by an electron-withdrawing group at the o- or p-position is replaced with an alcohol or a phenol (for example, Journal of. polymer·
Science. , Polymer Chemistry Edition (J. Polym. Sci., Polym. Chem.
Ed), 15 , 2441 (1977); Journal of Organic Chemistry (J. Org. Che).
m. ), 39 , 1839 (1974); Journal of Polymer Science. , Polymer Chemistry Edition (J. Polym. Sci., Poly
m. Chem. Ed), 18 , 3069 (1980) and tetrahedron (Tetrahedrom.) 34 , 205.
There are 7 (1978) reviews. However, regarding the reaction of a non-activated nitro group such as m-dinitrobenzene, only some examples of substitution reaction with alcohols are known.

For example, (1) a method of producing m-nitroanisole by reacting m-dinitrobenzene and sodium methoxide in a hexamethylphosphotriamide (HMPA) solvent at 25 ° C. for 16 hours (Journal of Garnic Chemistry (J . Org. Chcm.) 41 , 1560 (1
976)), (2) in the presence of a macrocyclic polyether, in a polar organic solvent, m
-A method of reacting dinitrobenzene with an alkoxide of an alkali metal to produce m-nitrophenyl alkyl ether (JP-A-54-39030), (3) Phase transfer of m-dinitrobenzene and sodium methoxide in chlorobenzene. React in the presence of a catalyst,
Method for producing m-nitroanisole (Chemistry
And Industry (Chem. & Ind.), 1
982, 412) are known. However, since these use special and expensive compounds such as HMPA and crown ethers, it is difficult to say that they are general reactions.

Recently, as a method for improving these, m-dinitrobenzene and alcohols were reacted in the presence of an alkali metal carbonate, hydrogen carbonate, trialkali metal phosphate or carbon dioxide gas to give m-nitrophenyl. A method for producing an alkyl ether has also been reported (JP-A-58-1804).
1, ibid. 59-25353 and ibid. 59-44343).

On the other hand, regarding the substitution reaction of m-dinitrobenzene with phenols, conventionally, in the presence of a macrocyclic polyether,
Only a method for producing 3-nitrodiphenyl ethers by reacting m-dinitrobenzene with an alkali metal salt of phenols in a polar organic solvent is known (Japanese Patent Laid-Open No. 39390/1979).

However, in this case, it is necessary to use a special reagent such as crown ether, which is expensive and is known to be toxic, as a reaction accelerator, and there is a drawback that its recovery is difficult. ing. As described above, the substitution reaction of m-dinitrobenzene with phenols is expected to be considerably difficult as compared with the case of alcohols, and there has been no conventional example under usual industrially conceivable conditions.

(Problems to be Solved by the Invention) As described above, the problem of the present invention is
-Overcoming the difficulties expected from the production example of 3-nitrodiphenyl ethers by the condensation reaction of dinitrobenzene and phenols, in particular by condensing bisphenol having two hydroxyl groups with m-dinitrobenzene, M-APAI which is a raw material of useful polyimide resins, etc. by producing (3-nitrophenoxy) compound and reducing it
Is to provide at low cost.

(Means for Solving the Problems) In order to solve the problems of the present invention, the inventors of the present invention have conducted extensive studies and as a result, m-dinitrobenzene and 1- (4-hydroxyphenyl) -1,3,3 By condensing -trimethyl-6-hydroxyindane with a base using an aprotic polar solvent, a bis (3-nitrophenoxy) compound can be obtained from the yield, and m-
The present invention has been completed by finding that APAI can be easily produced.

That is, the present invention provides 1) Formula (1) 1- [4- (3-aminophenoxy) phenyl] -1,3,3-trimethyl-6- (3-aminophenoxy) indane represented by

2) m-dinitrobenzene and formula (2) 1- (4-hydroxyphenyl) -1, represented by
3,3, -trimethyl-6-hydroxyindane was reacted in the presence of a base in an aprotic polar solvent to give the compound of formula (3) A 1- [4- (3-nitrophenoxy) phenyl] -1,3,3-trimethyl-6- (3-nitrophenoxy) indane represented by the formula (1) ) Represented by 1- [4- (3-aminophenoxy) phenyl] -1,3,3-trimethyl-6- (3-aminophenoxy) indane.

The present invention will be described in more detail.
The method for obtaining PAI consists of two steps, a condensation step and a reduction step. First, in the condensation process, m-dinitrobenzene and 1- (4-hydroxyphenyl) represented by the formula (2) are used as raw materials.
-1,3,3-Trimethyl-6-hydroxyindane is reacted with an aprotic polar solvent in the presence of a base. As a result, 1- [4- (3-nitrophenyl) phenyl] -1,3,3-trimethyl-represented by the formula (3)
6- (3-Nitrophenyl) indane is produced. The raw material 1- [4- (3-hydroxyphenyl) -1,3,3-trimethyl-6-hydroxyindane used in this condensation step is 4-isopropenylphenol or 4-isopropenylphenol.
It can be easily prepared by treating a linear dimer of isopropenylphenol with a fixed acid catalyst (Mimaki et al., JP-A-50-35150).

The base is an alkali metal carbonate, hydrogen carbonate, hydroxide or alkoxide, such as potassium carbonate,
Sodium carbonate, potassium hydrogen carbonate, potassium hydroxide,
Examples thereof include sodium hydroxide, lithium hydroxide, sodium methoxide, potassium isopropoxide and the like. Of these, potassium carbonate is particularly preferably used,
It is potassium hydrogen carbonate.

The amount of the base used is not particularly limited, and it is usually 2 to 5 equivalents with respect to bisphenol as a raw material, and preferably 2.5.
~ 3.5 equivalents are sufficient.

Next, an aprotic polar solvent is used as the reaction solvent in this method. Examples of the aprotic polar solvent include N-methylformamide, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, dimethylsulfone, sulfolane, N-methylpyrrolidone, 1,3-dimethyl-2-imidazo. Examples thereof include ridinone and hexamethyltriamide phosphate. The amount of these solvents used is not particularly limited, but usually 1 to 10 times the weight of the raw materials is sufficient.

The reaction temperature is usually 80 to 220 ° C., preferably 120.
Is in the range of 180 ° C.

A general embodiment of this first stage reaction is:
There is no particular limitation such as a charging method of raw materials, and a predetermined amount of m-dinitrobenzene, 1- (4-hydroxyphenyl) -1,
3,3-Trimethyl-6-hydroxyindane, a base and an aprotic polar solvent are charged and reacted under a stream of an inert gas such as nitrogen gas.

The end point of the reaction can be determined by thin layer chromatography, high performance liquid chromatography or the like. After completion of the reaction, after distilling off the solvent or discharging the reaction solution as it is into water, a crude product of an intermediate compound bis (3-nitrophenoxy) compound is obtained, and the crude product should be purified by recrystallization or the like. You can

In this first-stage reaction, quaternary ammonium salt, 4
-Grade phosphoric acid, macrocyclic polyether such as crown ether, nitrogen-containing macrocyclic polyether such as cryptate,
Phase transfer catalysts such as nitrogen-containing chain polyethers, polyethylene glycol and its alkyl ethers, copper powder and copper salts may be added as reaction accelerators.

The bis (3-nitrophenoxy) compound obtained in the first stage reaction is then subjected to the second stage reduction reaction.

The reduction method used in the second stage reaction is not particularly limited,
Usually, a method of reducing a nitro group to an amino group (for example, New Experimental Chemistry Course, Volume 15, Oxidation and Reduction [II], Maruzen (19
Although 77)) can be applied, catalytic reduction or hydrazine reduction is industrially preferable. In the case of catalytic reduction, the reduction catalyst used is a metal catalyst generally used for catalytic reduction, such as nickel, palladium, platinum, rhodium,
Ruthenium, cobalt, copper, etc. can be used. It is industrially preferable to use a palladium catalyst. These catalysts can be used in a metal state, but usually, they are used by supporting them on a carrier surface such as carbon, barium sulfate, silica gel, alumina, and celite, and nickel, cobalt, copper, etc. It is also used as a catalyst. The amount of the catalyst used is not particularly limited, but is in the range of 0.01 to 10% by weight as a metal with respect to the bis (3-nitrophenoxy) compound as a raw material, and usually 2 when used in a metal state. -8% by weight, and 0.1 to 5% by weight when loaded on a carrier.

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, ethers, dioxane and tetrahydrofuran. , Ethers such as methyl cellosolve are preferably used, and in some cases, aliphatic hydrocarbons such as hexane and cyclohexane, aromatic hydrocarbons such as benzene, toluene and xylene, esters such as ethyl acetate and butyl acetate, Halogenated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, 1,1,2-trichloroethane, tetrachloroethane and N, N-dimethylformamide can also be used. When a reaction solvent which is immiscible with water is used and the reaction progresses slowly, it can be accelerated by adding a commonly used phase transfer catalyst such as a quaternary ammonium salt or a quaternary phosphonium salt. The amount of the solvent used is not particularly limited as long as it is sufficient to suspend or completely dissolve the raw material, but 0.5 to 10 times by weight of the raw material is usually sufficient.

The reaction temperature is not particularly limited. Generally 20-200
The range of ° C, especially 20 to 100 ° C is preferable. The reaction pressure is usually from atmospheric 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.

On the other hand, in the case of hydrazine reduction, hydrazine is usually
The reduction reaction may be carried out in a slight excess, preferably 1.2 to 2 times the theoretical amount.

As the catalyst, the above metal catalyst generally used for catalytic reduction is used. Industrially, a catalyst in which palladium / carbon, platinum / carbon or ferric chloride is adsorbed on activated carbon is preferable. The amount of catalyst used is not particularly limited,
Usually, it is in the range of 0.01 to 30% by weight as a metal with respect to the raw material bis (3-nitrophenoxy) compound.

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.

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

After completion of the reaction, the reaction solution is heated to remove the catalyst, and then the solvent is distilled off if necessary to obtain a desired crude product of m-APAI. This crude product can be purified by recrystallization or isolation as a mineral acid salt.

(Operation and Effect) The present invention provides a novel and useful diamine monomer and a method for producing the same. Since this diamine monomer has a stable indane structure and an ether bond in the molecule, the polyimide resin using this monomer has extremely good thermal stability.

In addition to the extremely useful feature that the polyimide resin using this monomer can be molded and processed, it has the feature that it is soluble in a solvent, which is not present in conventional polyimide resins.

That is, the above polyimide resin is soluble in aprotic polar solvents, ether solvents, halogenated hydrocarbon solvents, etc., and as a result, is simply imidized in the solvent and then cast and dried, and is called a void. A homogeneous film with no pores can be produced.

Further, this polyimide resin can be used as an adhesive as well as a molding material, for example, an adhesive varnish such as polyimide resin, copper, aluminum, titanium and ceramics, an adhesive powder, an adhesive film and the like can be supplied at low cost.

The method for producing m-APAI of the present invention is an industrially suitable production method that can produce a high-purity diamine monomer inexpensively in a high yield with a simple work process using an inexpensive starting material.

(Examples) The present invention will be described in more detail with reference to Examples.

Example 1 1 in a reactor equipped with stirrer, thermometer and reflux condenser
-(4-Hydroxyphenyl) -1,3,3-trimethyl-6-hydroxyindane 67.1 g (0.25 mol), m-dinitrobenzene 100.9 g (0.6 mol), anhydrous potassium carbonate 69.1 g (0.5 mol) and N, N-dimethylformamide (650 ml) were charged, and the reaction was carried out with stirring while nitrogen gas was passed through. The reaction was carried out at a temperature of 150 to 153 ° C. for 7 hours to complete the reaction.

After completion of the reaction, excess inorganic salts were removed and the mixture was concentrated under reduced pressure with an evaporator. The concentrated residue was a brown oily substance, and 280 ml of methyl cerolube and 20 ml of water were added and dissolved by heating to be crystallized. After this is washed, washed and dried, 112.5 g of 1- [4- (3-nitrophenoxy) phenyl] -1,3,3-trimethyl-6- (3-
Nitrophenoxy) indane was obtained (yield 88.1).
%).

This was recrystallized with ethanol to give pure yellow needle-like 1-
[4- (3-nitrophenoxy) phenyl] -1,3,
3-Trimethyl-6- (3-nitrophenoxy) indane was obtained. The melting point is 90 to 92 ° C., and the results of elemental analysis are as follows.

Then, the above-mentioned 1- [4- (3-nitrophenoxy) phenyl]-was placed in a closed reduction reactor equipped with a stirrer and a thermometer.
1,3,3-Trimethyl-6- (3-nitrophenoxy) -indane 10.21 g (0.02 mol), 5% P
Charge 0.3 g of d / c contact and 30 ml of ethanol,
Hydrogen gas was introduced with vigorous stirring.

When the reaction temperature was 62 to 68 ° C. for 4 hours, 2760
After absorbing ml of hydrogen and no more absorption was observed, the reaction was terminated. After completion of the reaction, the catalyst was removed by passing and the solvent was recovered by concentrating with an evaporator.

Next, 6.5 g of concentrated hydrochloric acid and 50 ml of a 20% isopropanol aqueous solution were added to the concentrated residue, and the mixture was heated and dissolved, and then activated carbon was added and heated.

When this excess was dropped into diluted ammonia water, a precipitate was deposited. This is 1- [4- (3-aminophenoxy) phenyl] -1,3,3-trimethyl-6- (3-
It was aminophenoxy) indane, washed and dried to obtain 8.5 g (yield 94.3%). Melting point 70-72
℃ Example 2 By the method of Example 1, 80 g (0.8 mol) of anhydrous potassium hydrogen carbonate was used as anhydrous potassium carbonate, and 1,3-dimethyl-2-imidazolidinone 80 was used as N, N-dimethylformamide.
The reaction mixture was replaced with 0 ml and the reaction was carried out at a reaction temperature of 160 to 165 ° C. for 5 hours to give the intermediate 1- [4- (4-nitrophenoxy) phenyl] -1,3,3-trimethyl-6- (3-nitrophenoxy) indane 108. 0.8 g was obtained (yield 85.2).
%).

The nitro compound was charged into a reduction reactor together with 2.0 g of 5% Pt / C catalyst and 300 ml of isopropanol, and hydrogen was introduced with vigorous stirring for reduction.

After the completion of the reaction, excess contact was removed, and 200 g of a 15% aqueous sulfuric acid solution was added dropwise to the solution to precipitate a sulfate of m-APAI. After this was washed with water and neutralized with stirring in dilute ammonia water, crystals of the target product, m-APAI, were deposited. After filtration, washing with water and drying, 82.6 g was obtained (total yield: 73.3%).

Melting point 68 to 71 ° C. Example 3 1- [4- (3-Nitrophenoxy) phenyl] -1,3,3-trimethyl-6 was prepared in the same manner as in Example 1 except that the solvent was changed to dimethyl sulfoxide. -(3-
102.3 g of nitrophenoxy) indane was obtained (yield 80.1%).

Example 4 1- [4- (3-Nitrophenoxy) obtained in Example 1 in a reactor equipped with stirrer, thermometer and flow-through cooler
Phenyl] -1,3,3-trimethyl-6- (3-nitrophenoxy) indan 12.8 g (0.025 mol), ferric chloride 0.1 g, activated carbon 1.5 g and methyl cellosolve 30 ml were charged. At a temperature of 100 to 105 ° C., 5 g (0.1 mol) of hydrazine hydrate was added dropwise over 1 hour. After the dropping was completed, the reaction was continued for 4 hours at the same temperature to complete the reaction.

After 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 9.5 g of m-APAI. (Yield 84.3
%). The melting point was 70-72 ° C.

Example 5 1- [4- (3-Nitrophenoxy) phenyl] -1,3,3-trimethyl-6- (3-obtained in Example 1
12.8 g of nitrophenoxy) indane, 1 g of Raney nickel catalyst and 50 ml of diglyme were charged into an autoclave, and reduction reaction was carried out at a temperature of 80 to 90 ° C. and a hydrogen pressure of 30 kg / cm ^{2 for} 1 hour. The post-treatment after the reaction was carried out in Example 1.
The same procedure as in (3) was performed to obtain 9.3 g of the desired product. Yield 8
It had a melting point of 70-72 ° C at 2.5%.

Reference Example 1 1 in a container equipped with a stirrer, a reflux condenser and a nitrogen introducing pipe
-[4- (3-aminophenoxy) phenyl] -1,
3,3-Trimethyl-6- (3-aminophenoxy) indan 45.0 g (0.1 mol) and N, N'-dimethylacetamide 200.4 g were charged, and pyromellitic acid was added at room temperature under a nitrogen atmosphere. 21.8 g of dianhydride (0.
1 mol) was added portionwise while being careful that the solution temperature did not exceed 30 ° C., and the mixture was stirred at room temperature for about 20 hours.

In the N, N'-dimethylacetamide solution of the obtained polyamic acid, the logarithmic viscosity at 35% and 0.5% concentration was 146.
It was dl / g. After taking a part of this polyamic acid solution and casting it on a glass plate, 100 ° C., 200 ° C., 30
Each was heated at 0 ° C. for 1 hour to obtain a pale yellow transparent polyimide film. The glass transition temperature of this polyimide film was 237 ° C. (measured by TMA penetration method), and the 5% weight loss temperature was 503 ° C. (measured by DTA · TG). Further, this polyimide film was preheated to 130 ° C. steel (cold rolled steel, JIS G3141, Spec /
SD, 25 x 100 x 1.6 mm) and insert between 340
Pressure was applied at 20 ° C. and 20 kg / cm ² for 5 minutes. The tensile shearing force of this product at room temperature was 320 kg / cm ² .

(The measuring method is JIS K-6848 and K-6850.
According to. ) Further, 67 g of N, N'-dimethylacetamide was added to 100 g of the polyamic acid solution, and the mixture was heated to 70 ° C under a nitrogen atmosphere with stirring, and then 9.2 g (0.09 mol) of acetic anhydride and 2.3 g (0 (0.023 mol) of triethylamine was added dropwise and the reaction was carried out for 2 hours. This solution was cooled and then discharged into 850 g of water to obtain a pale yellow powder precipitate.

After separating this precipitate, it was dried at 150 ° C. for 10 hours, and 21.
9 g (yield 98%) of pale yellow powder was obtained.

The powder thus obtained was confirmed to be polyimide by IR analysis.

A part of this polyimide powder was taken and dissolved in N, N'-dimethylacetamide so as to be 20 wt% to obtain a polyimide solution. This polyimide solution was cast on a glass plate and then heated at 100 ° C. and 200 ° C. for 1 hour to obtain a pale yellow transparent polyimide film having excellent flexibility. In addition, the above polyimide powder is applied at 330 ° C. for 15 minutes 15
It was molded under a pressure of 0 kg / cm ² . This molded product was a light brown transparent molded product excellent in flexibility.

Claims (2)

[Claims] 1. A formula (1) 1- [4- (3-aminophenoxy) phenyl] -1,3,3-trimethyl-6- (3-aminophenoxy) indane represented by 2. m-Dinitrobenzene and formula (2) 1- (4-hydroxyphenyl) -1, represented by
Reaction of 3,3-trimethyl-6-hydroxyindane in the presence of a base in an aprotic polar solvent (3) 1- [4- (3-nitrophenoxy) phenyl] -1,3,3,3-trimethyl-6- (3-nitrophenoxy) indane represented by the formula 1- [4] A method for producing-(3-aminophenoxy) phenyl] -1,3,3-trimethyl-6- (3-aminophenoxy) indane.