JPH06729B2 - 6,6'-bis (3-aminophenoxy) -3,3,3 ', 3'-tetramethyl-1,1'-spirobiindane and method for producing the same - Google Patents

Description

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

(Technical Background of the Invention) This 6,6′-bis (3-aminophenoxy) -3,
3,3 ', 3'-Tetramethyl-1,1'-spirobiindane (hereinafter abbreviated as m-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 (4,4'-diaminodiphenyl ether and pyromellitic dianhydride) (Dupont, trade name "Vespel") is insoluble and infusible, and therefore has a special feature called powder sintering molding. The method is used.

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

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, they have excellent heat resistance (Coating & Plastics (Coating & Plastics
Preprints), 35 (2) 77-82 (1975)), but 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 focused their attention on the indane structure having such characteristics, and further introduced an aromatic ether bond, m-.
It was expected that a polyimide resin having excellent flexibility and molding processability could be obtained if the diamine at the higher position could be produced.

As a result, it was found that the m-BASI according to the present invention was successfully produced, and the polyimide resin using the same has the expected performance.

That is, the polyimide resin composed of m-BASI and pyromellitic dianhydride has a relatively low glass transition temperature of 253 ° C. and has a heat resistance of 5 ° C. and a weight loss of 5% in air of 500 ° C.
Thus, the molding processability and the thermal stability were excellent. A very useful polyimide resin was obtained.

(Prior Art) Heretofore, this m-BASI has never been synthesized and its manufacturing method has not been known.

The m-BASI of the present invention can be produced by condensing m-dinitrobenzene and bisphenol having an indane ring to obtain a bis (3-nitrophenoxy) compound and reducing it.

Heretofore, in an aromatic nitro compound, many reactions have been known in which an nitro group activated by an electron-withdrawing group at the o- or p-position is substituted with an alcohol phenol (for example, HM, Relles). Et al., Journal of Polymer Science, Polymer Chemistry Edition (J.Polym.Sci., Polym.Chem.Ed.), 1
5 , 2441 (1977); R. Beck et al., Journal of Organic Chemistry (J.Org.Chem.), 39 , 183.
9 (1974); Takekoshi et al., Journal of Polymer Science Polyar Chemistry.
Edition (J.Polym.Sci., Polym.Chem.Ed.), 1
8 , 3069 (1980) and J. R. Beck. , Tetrahedrom, 34 , 2057 (1978) for review). However, regarding the reaction of a non-activated nitro group such as m-dinitrobenzene, only some examples of the 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 (N. Kornblum et al., Journal of・ Garnic Chemistry (J.Org.Chcm.),
41 , 1560 (1976)), (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 (Toyoda et al., JP-A-54-39030), (3) m-dinitrobenzene and sodium methoxide in chlorobenzene. , A method for producing m-nitroanisole by reacting in the presence of a phase transfer catalyst (F. Montanar
i et al., Chemistry & Industry (Chem. & I
nd.), (1982), 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-58-18041, 59-59).
-2535 and 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 (JP-A-54-39030).

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 with phenols, in particular by condensing bisphenol having two hydroxyl groups with m-dinitrobenzene, M-BASI which is a raw material for useful polyimide resins, etc. by producing a (3-nitrophenoxy) compound and reducing it
Is to provide at low cost.

(Means for Solving the Problems) In order to solve the problem of the present invention, the inventors of the present invention have conducted extensive studies and as a result, m-dinitrobenzene and 6,6′-dihydroxy-3,3,3 ′, 3'-tetramethyl-1,
By condensing 1'-spirobiindane base with an aprotic polar solvent, a bis (3-nitrophenoxy) compound can be obtained from the yield, and m-BASI of the target compound can be easily produced by reducing it. Then, the present invention has been completed.

That is, the present invention has the formula (1) 6,6'-bis (3-aminophenoxy) represented by
-3,3,3 ', 3'-tetramethyl-1,1'-spirobiindane and a compound of the formula m-dinitrobenzene
(2) 6,6'-dihydroxy-3,3,3 ', represented by
By reacting 3'-tetramethyl-1,1'-spirobiindane in the presence of a base in an aprotic polar solvent, the formula
(3) 6,6'-bis (3-nitrophenoxy) represented by
This is a method of producing -3,3,3,3 ', 3'-tetramethyl-1,1'-spirobiindane and further reducing it.

The present invention will be described in detail. The target compound, m-BA
The method of obtaining SI consists of two processes, a condensation process and a reduction process. First, in the condensation process, m-dinitrobenzene and 6,6'-dihydroxy-3,3,3 represented by the formula (2) are used as raw materials.
3 ', 3'-Tetramethyl-1,1'-spirobiindane is reacted in the presence of a base with an aprotic polar solvent. As a result, 6,6'-bis (3-nitrophenoxy) -3,3,3 ', 3'-tetramethyl-1,1'-spirobiindane represented by the formula (3) is produced.

The raw material 6,6'-dihydroxy-3,3,3 ', 3'-tetramethyl-1,1'-spirobiindane used in this condensation process is 2,2-bis (4-hydroxyphenyl) propane in sulfuric acid or It can be produced by heat treatment with concentrated hydrochloric acid (US Pat. No. 3271473).

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 and potassium hydrogen carbonate are particularly preferably used.

The amount of the base used is not particularly limited, and it is usually 2 to 5 equivalents relative to the raw material bisphenol, preferably 2.5 to
3.5 equivalents is 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 on the charging method of the raw materials, and a predetermined amount of m-dinitrobenzene, 6,6′-dihydroxy-3,3,3 ′,
3'-Tetramethyl-1,1'-spirobiindane, a base and an aprotic polar solvent are charged and the reaction is carried out 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 (eg, New Experimental Chemistry Course, Volume 15, Oxidation and Reduction [II], Maruzen (197
Although 7)) 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 or the like can be used. It is industrially preferable to use a palladium catalyst. These catalysts can be used in a metal state, but usually, carbon,
It is used by supporting it on the surface of a carrier such as barium sulfate, silica gel, alumina or celite, and nickel, cobalt, copper or the like is also used as a Raney 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, 0.1 to 5% by weight when loaded on a carrier
Is the range.

The reaction solvent is not particularly limited as long as it is inert to the reaction, for example, 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 and 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 usually 0.5 to 10 times by weight of the raw material is 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 concentration 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-BASI. 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 spirobiindane structure and an ether bond, the polyimide resin using this monomer has extremely good thermal stability.

Further, the polyimide resin using this monomer has a feature that it can be molded.

In addition to molding materials, applications as adhesives, for example, adhesive varnishes such as polyimide resin, copper, aluminum, titanium and ceramics, adhesive powders, adhesive films, etc. can be supplied at low cost.

The method for producing m-BASI of the present invention is an industrially suitable production method capable of producing a high-purity diamine monomer with a high yield in 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 77.1 g (0.25 mol) of 6,6'-dihydroxy-3,3,3 ', 3'-tetramethyl-1,1'-spirobiindane was added to a reactor equipped with a stirrer, a thermometer and a reflux condenser. , 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 completed under stirring while aeration with nitrogen gas. After the reaction is complete, water
When diluted with 650 ml, a light brown precipitate was deposited. The precipitate was filtered, washed with isopropanol and dried.
This is 6,6'-bis (3-nitrophenoxy) -3,
It was 3,3 ', 3'-tetramethyl-1,1'-spirobiindane, and the yield was 116.5 g (yield 84.6%).

This was recrystallized with ethanol to give pure brown needle-like 6,
6'-bis (3-nitrophenoxy) -3,3,3 ',
3'-Tetramethyl-1,1'-spirobiindane was obtained. The melting point is 173.5 to 175 ° C, and the results of elemental analysis are as follows.

Next, the above-mentioned 6,6'-bis (3-nitrophenoxy) -3,3,3 was placed in a closed reduction reactor equipped with a stirrer and a thermometer.
11 g (0.02 mol) of 3 ', 3'-tetramethyl-1,1'-spirobiindane, 0.3 g of 5% Pd / C and 40 ml of methyl cellosolve were charged, and hydrogen gas was introduced with vigorous stirring.

When the reaction was carried out at a reaction temperature of 70 to 80 ° C. for 8 hours, 2650 ml of hydrogen was absorbed and no further absorption was observed, so the reaction was terminated. After completion of the reaction, the catalyst was removed by heating to remove the catalyst, and the mixture was diluted with 50 ml of isopropanol to precipitate crystals. This was filtered, washed with isopropanol and dried. The white needle-like crystals obtained were 6,6'-bis (3-aminophenoxy) -3,3,3 ', 3'-tetramethyl-1,1'-spirobiindane, and the yield was 7.5 g.
(Yield 76.4%) and the melting point was 205 to 206 ° C.

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

NMR spectrum Measurement solvent: Acetone D-6 Measurement temperature: Room temperature 1.4ppm (12H doublet) 2.2 to 2.5ppm (4H multiplet) 6.0 to 6.5ppm (8H multiplet) 6.7 to 7.3ppm (6H multiplet) MS spectrum (M / e) M ⁺ 490, 475, 238, 65 Example 2 According to the method of Example 1, 80 g (0.8 mol) of anhydrous potassium hydrogen carbonate and 1,3 of N, N-dimethylformamide were added. -Dimethyl-2-imidazolidinone 80
The reaction mixture was replaced with 0 ml and the reaction was carried out at a reaction temperature of 170 to 175 ° C. for 10 hours to obtain the intermediate 6,6′-bis (3-nitrophenoxy).
112 g of -3,3,3 ', 3'-tetramethyl-1,1'-spirobiindane was obtained (yield 81.4%).

11 g of this nitro compound was charged in a reduction reactor together with 0.2 g of 5% Pt / C catalyst and 100 ml of ethanol, and hydrogen was introduced with vigorous stirring for reduction.

After completion of the reaction, the catalyst was removed by passing, the mixture was concentrated, and 75 g of a 15% hydrochloric acid aqueous solution was added dropwise to precipitate m-BASI hydrochloride. After this was washed with water and neutralized with stirring in dilute ammonium water, crystals of the target product, m-BASI, were precipitated. After washing with water and drying, 8.75 g was obtained (yield 8
9.2%).

Melting point 205 to 206 ° C. Example 3 6,6′-Bis (3-nitrophenoxy) -3,3,3 ′, 3′- was carried out in the same manner as in Example 1 except that the solvent was changed to dimethyl sulfoxide. Tetramethyl-1,
110 g of 1'-spirobiindane was obtained (yield 79.9
%).

Example 4 The 6,6'-bis (3-nitrophenoxy) -3,3,3 ', 3'-tetramethyl-obtained in Example 1 was placed in a reactor equipped with a stirrer thermometer and a reflux condenser. 1,1'-
Spirobiindane 13.8 g (0.025 mol), ferric chloride 0.1
g, 1.5 g of activated carbon and 30 ml of methyl cellosolve were charged, and 5 g of hydrazine hydrate (0.
1 mol) 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 the completion of the reaction, the catalyst was post-treated in the same manner as in Example 1 except that the catalyst was not used.
0.1 g of m-BASI was obtained (yield 82.3%). Melting point is 2
It was 03-206 ° C.

Example 5 6,6′-Bis (3-nitrophenoxy) -3,3,3 ′, 3′-tetramethyl-1,1 ′ obtained in Example 1
-Spirobiindane 13.8 g, Raney nickel catalyst 1
g and 50 ml of diglyme into an autoclave,
The 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. Post-treatment after the reaction was carried out in the same manner as in Example 1 to obtain 10.5 g of the desired product. The yield was 85.6% and the melting point was 203 to 206 ° C.

Reference Example 1 6,6′-bis (3-aminophenoxy) -3,3,3 was placed in a container equipped with a stirrer, a reflux condenser and a nitrogen inlet tube.
49.0 g (0.10 M) of 3 ', 3'-tetramethyl-1,1'-spirobiindane and N, N-dimethylacetamide 2
Charge 11 g, and in a nitrogen atmosphere at room temperature, add 21.36 g (0.098 M) pyromellitic dianhydride at a solution temperature of 30 ° C.
Be careful not to exceed the limit and add in 20 at room temperature.
Stir for hours.

The polyamic acid thus obtained had a logarithmic viscosity at 0.5% in a solvent of N, N-dimethylacetamide at 35 ° C. of 0.79 dl /
It was g. A steel plate (cold rolled steel, JIS G31) obtained by washing this polyamic acid solution with trichlorethylene.
No. 41, spec / sb, 25 × 100 × 1.6, the same applies below), heat-dry at 100 ° C. for 1 hour and 220 ° C. for 1 hour, stack steel plates, and then add 5 at 340 ° C., 20 kg / cm ² . It pressure-bonded for a minute. The tensile shear force of this thing is
It was 250 kg / cm ² at room temperature and 180 kg / cm ² at a high temperature of 240 ° C. (Measurement method is JIS K-6
848 and 6850. The same applies to the following.) A part of this polyamic acid solution was cast, cast on a glass plate, and then heated at 100 ° C, 200 ° C, and 300 ° C for 1 hour to obtain a polyimide film. The glass transition temperature of this polyimide film was 253 ° C. (measured by the TAM penetration method, the same applies hereinafter), and the 5% weight loss temperature in air was 501 ° C. (measured by DAT-TG, apply the same below). .

Claims (2)

[Claims] 1. A formula (1) 6,6'-bis (3-aminophenoxy) represented by
-3,3,3 ', 3'-Tetramethyl-1,1'-spirobiindane. 2. m-Dinitrobenzene and formula (2) 6,6'-dihydroxy-3,3,3 ', represented by
3'-Tetramethyl-1,1'-spirobiindane is reacted in the presence of a base in an aprotic polar solvent to give a compound of the formula
(3) 6,6'-bis (3-nitrophenoxy) represented by
-3,3,3 ', 3'-Tetramethyl-1,1'-spirobiindane is produced and further reduced to give 6,6'-bis (3 -Aminophenoxy) -3,3,3 ', 3'-tetramethyl-
Process for producing 1,1'-spirobiindane.