JPS6284049A - Production of aromatic diamine solution for polymerization - Google Patents

Abstract

PURPOSE:To produce the titled compound useful as a heat-resistant polymeric material at a remarkably reduced production cost in extremely improved working environment, by reacting a solution of an aromatic diamine with an aromatic carboxylic acid chloride in polar amide solvent. CONSTITUTION:An aromatic diamine solution is produced by carrying out the catalytic reduction of an aromatic dinitro compound or an aromatic mononitroamino compound in a polar amide solvent free from inhibiting activity to the polymerization reaction (e.g. N,N-dimethylformamide) in the presence of a heterogeneous hydrogenation catalyst (e.g. platinum-carbon) and removing by-produced water by distillation. The solution is made to react with an aromatic tricarboxylic acid anhydride monochloride of formula I (Ar is trivalent aromatic residue) and/or an aromatic dicarboxylic acid dichloride of formula II (Ar' is bivalent aromatic residue) in a polar amide solvent at 20-200 deg.C to obtain the objective product.

Description

[Detailed Description of the Invention] <Industrial Application Field> The present invention provides a method for producing an aromatic diamine solution that can be used directly in a polymerization process without isolating aromatic diamines from a hydrogenation process. It is related to.

<Prior Art> Aromatic diamines have been widely put into practical use as essential components for the production of heat-resistant polymers. Recently, the need for high-performance polymer materials has been rapidly increasing in the field of advanced industrial technology.
The wings are played by various heat-resistant polymer groups. In this sense, the importance of aromatic noamino compounds in industry is increasing.

Heat-resistant polymers are generally prepared by combining aromatic diamines and bifunctional aromatic acidic compounds, such as pyromellitic dianhydride and trimellitic anhydride monopropylene, in an amide polar solvent under anhydrous conditions at room temperature. Chloride, terephthalic acid dichloride,
It is synthesized by reacting isophthalic acid dichloride etc.

Traditionally, aromatic diamines have been produced by subjecting aromatic dinitro compounds to catalytic hydrogen reduction in a polar solvent, followed by addition! ! 8
/ After hot filtration, it has been widely used to concentrate and crystallize as necessary for isolation. In other words, the British patent number 1.
No. 228.738.

JP-A-56-22,752, JP-A-57-176
．． Publication No. 935, etc.

Industrially, aromatic diamines have been supplied in the form of dry powder or flakes.

<Problems to be Solved by the Invention> However, aromatic diamines are generally mutagen-positive substances (suspects of developing cancer), so special strict environmental measures are required when handling them.

However, since it is handled in the form of powder or flakes, it inevitably generates fine dust, and there are limits to environmental measures. A quick way for aromatic diamine users to solve this problem was to have the aromatic diamine manufacturer dissolve the aromatic diamine in a polymerization solvent and obtain the aromatic diamine as a solution. . However, as long as aromatic diamine manufacturers isolate and handle aromatic diamines, this method merely shifts the powder layer handling work from the user side to the manufacturer side, and is not a fundamental solution. It's obvious.

Therefore, the present inventors have conducted intensive studies with the aim of utilizing aromatic diamine directly in the polymerization process without isolating it from the aromatic diamine manufacturing process, and as a result, they have arrived at the present invention.

Means for Solving the Problems> That is, the present invention involves contacting an aromatic dinitro compound or an aromatic mononitroamino compound in the presence of a heterogeneous hydrogenation catalyst in an amide polar solvent that does not inhibit the polymerization reaction. The present invention provides a method for producing an aromatic diamine solution for polymerization, which is characterized in that after reduction, by-product water is removed by distillation.

The amide-based polar solvent used in the present invention is a polar solvent that does not exhibit the property of inhibiting the expansion of the degree of polymerization between the aromatic diamine compound and the bifunctional aromatic acidic substance, and has an amide bond in the molecule, - For example, N-N-dimethylacetamide, N·N-dimethylacetamide, N-methylpyrrolidone, N-ethylpyrrolidone% N-butylpyrrolidone, N-cyclohexyl V/L/pyrrolidone, N-methylpiperidone, 1,3-dimethyl /l/ -2-imidazolidinone, hexamethylphosphoramide and the like. Particularly useful are N-methylpyrrolidone and N-N-dimethylacetamide. Furthermore, N-N-dimethylformamide, which is a similar compound, has a polymerization inhibiting effect and cannot be used for the purpose of the present invention.

The aromatic dinitro compound or aromatic mononitroamino compound used in the present invention has the general formula 02 L'J Ar
It is a compound represented by S02 or 02 N Ar NHz, where -Ar- represents a divalent aromatic residue selected from the general formula. Here, R1 is an anosyl group or alkoxy group having 1 to 4 carbon atoms, and X is a direct bond -〇-1
-S-1CHs CFs Q 1l -N-C-, a represents 0 or an integer of 1 to 4, and b represents 0 or an integer of 1 to 12. Specific examples of -Ar- are as follows.

i.e. 〒H・ F3 H.O. I II etc.

The heterogeneous hydrogenation catalyst used in the present invention is a metal or metal oxide catalyst generally used in catalytic reduction,
For example, platinum, palladium, rhodium,
Nickel μ, cobalt, copper, platinum oxide, palladium oxide,
Examples include rhodium oxide. These metal catalysts are
Although it can be used in the form of metal, it is usually attached to the surface of a carrier such as carbon, barium sulfate, silica gel, alumina, etc., and nickel, cobalt, copper, etc. are also used as Raney catalysts. The amount of catalyst used is 0.00 parts as metal content per 100 parts of the raw material nitro compound.
The amount is preferably 0.1 to 10 parts, and preferably 0.1 to 5 parts when attached to a carrier.

The reaction temperature is not particularly limited, but is generally 20 to 200°C.
The temperature range is preferably 50 to 130°C.

In addition, the pressure of hydrogen used in the reaction is 1 normal gauge pressure and O1
1 to 50 kg/α2, and the optimum range varies depending on the activity of the catalyst. For example, 5% palladium/activated carbon, 5%
For platinum/activated carbon, gauge pressure is 0.1 to 5 kg/cIA
” is appropriate, but in the case of Fune Nickel it is 10-50k
g/c112 is suitable.

In the hydrogenation reaction of the present invention, -NO□+3H2-NH2
The reaction of +2H20 produces 2 moles of water from 1 mole of NO2 groups.

In the present invention, following the hydrogenation reaction, the mother liquor is heated under steam pressure or reduced pressure to distill water as a low-boiling component, either while containing the insoluble catalyst or after the insoluble catalyst is collected by filtration. . At that time, it may be azeotropically distilled off with the solvent in the form of simple distillation, or it may be rectified through a rectification column.

It is also effective to use effective azeotropic aids such as benzene, toluene, xylene, and chlorobenzene. If the internal liquid layer becomes insufficient during the water distillation process, add a solvent and/or azeotropic aid from the outside to increase the water gold content in the mother liquor to 1 MM%, preferably 0.5% by weight, more preferably The distillation operation is continued until the concentration is 0.1% or less.

After completion of distillation removal of the by-product water, if necessary, insoluble components are temporarily removed to finally obtain an aromatic diamine solution suitable for polymerization. If the water content in this solution is 1% by weight or more, the polymerization activity when reacted with a difunctional aromatic acidic component is extremely low and cannot be used practically.

<Example> Hereinafter, the present invention will be explained in detail using Examples.

Example 1 In a glass autoclave with an internal volume of 1 liter, 26 g (0.1 mol) of 4°4'-dinitrodipheniate #, 0.8 g of 5% platinum carbon powder manufactured by Engelhard Japan, and N
- Charge 300ml of methyl-2-pyrrolidone, replace the air in the autoclave with nitrogen, and then heat to 201°2 with hydrogen.
0 kg/3 kg/via 3” gauge intermediate tank
The am gauge was pressurized. Next, the mixture was heated to 90° C. over 30 minutes with gentle stirring, and then the reaction was started with vigorous stirring. After that, there are 3
A hydrogen pressure of kg/3" gauge was maintained. Approximately 130 minutes after the start of strong stirring, the gauge pressure in the intermediate tank stopped decreasing, so stirring was continued for 1 hour to complete the reaction. Next, The contents were passed through a suction port to remove platinum-carbon powder and other insoluble matter, and the resulting filtration mother liquor was transferred to an Iβ flask equipped with a rectifying tube, a nitrogen gas introduction tube, and a stirrer, and nitrogen gas was passed through it. While adding 100 md of toluene, it becomes about 120 ~
The mixture was heated to 130° C., and water in the system was azeotropically distilled together with toluene. Subsequently, ioml of toluene was added, and finally all of the toluene actually purchased was distilled off to complete the dehydration operation.

The water content in the obtained dehydrated liquid was measured by the Karl Fischer method and was found to be 350 ppm.
When 4'-diami7diphenyl ether was analyzed by liquid chromatography and diazo method, the purity was 99.596. Yield: 99.
It was found to be 8%.

Next, 4.32 g of metaphenylene diamine (0,
04 mol) and placed in an ice water bath while stirring, 29.5 g of trimellitic anhydride monochloride in solid powder form was added.
((J, L 4 MoJv), when the internal temperature is 30
The polymer solution was added at a rate not exceeding 0.degree. C., and stirring was continued for 1 hour to obtain a polymer stock solution.

Next, this polymer stock solution was poured into 1O1 water under strong stirring to precipitate the polymer, which was then washed with water, dehydrated, and dried to obtain a polyamide-imide polymer powder.

Logarithmic viscosity ηinh of the obtained polymer (concentration: 0.5 g
/di, melt: N-me p-/l/-2 hyorin, temperature: 30°C) was measured and found to be 0.82, which is highly practical.

Comparative Example 1 All operations were performed in the same manner as in Example 1 except for omitting the dehydration operation, and the resulting polymer had ηinh of 0.29.
This was extremely low.

Comparative Example 2 PZ reaction: 'a g: N-methyl-2-pyrrolidone 3
N-N-dimethylformamide 30 instead of 00ml
0mj! The same operations as in Example 1 were carried out except that ηinh of the obtained polymer was 0.2.
It was extremely low at 5.

Example 2 26 g of 4,4'-dinitrodiphenyl ether (0,1
When the same operation as in Example 1 was performed except for using 4-nitro-3'-aminodiphenyl ether, u23g (0.1 mol), a highly practical product with ηinh of 0.86 was obtained. A polymer was obtained.

Example 3 Contents @ 1 g of glass autoclave 2,2-bis (4-nitrophenoquinphenyl) clopane H3 47.1 g (0.1 mol), Japanese Engel Ha tv l-
2g of 5% palladium-carbon powder made by n and N・N-
Tsumethylacetamide 400mJ? After t-charging and replacing the air in the autoclave with nitrogen, the autoclave was heated to 204 ml with hydrogen.
A pressure of 2 kg/Cl (12 gauge) was applied via an intermediate tank of 20 kg/am" gauge. Next, the mixture was heated to 80° C. with gentle stirring, and then the reaction was started with vigorous stirring. After that, there are 2
Hydrogen pressure of kg/cI 12 gauge was continued to be applied. About 3 hours after the start of strong stirring, the gauge pressure in the intermediate tank almost stopped decreasing, so stirring was continued for 2 hours to complete the reaction. Next, the contents were passed through a suction port to remove palladium-carbon powder and other insoluble matter, and the resulting filtration mother liquor was transferred to a 14 flask equipped with a rectification tube, a nitrogen gas introduction tube, and a stirrer. 1oorl of monochlorobenzene while flowing gas
was added and heated to about 140 to 150°C, and the water in the system was azeotropically distilled together with monochlorobenzene. Next is monochlorobenzene roomj? was further added, and finally substantially all of the monochlorobenzene was distilled off to complete the dehydration operation. The water content in the obtained dehydrated liquid was measured by the Karl Fischer method and found to be 2301) pm, and the produced 2,2-bis(4-aminophenoxyphenylene) V
) Propane was analyzed by liquid chromatography and diazo method and found to be 99.1% pure and 99.9% yield.

Next, the flask containing the above 2.2-bis(4-7minophenoxyphenyl/l/)propane solution was placed in an ice water bath and while stirring, solid powdered terephthalic acid dichloride/isophthalic acid dichloride (1/l) : f-le ratio) mixture 20
．． 3 g (0.1 mol) was added at such a rate that the internal temperature did not exceed 30° C., and stirring was continued for 1 hour to obtain a polymer stock solution. Next, this polymer stock solution was poured into 1O1 water under strong stirring to precipitate the polymer, and the polymer was washed with water, dehydrated, and dried by heating to obtain a polyamide polymer powder. The obtained polymer had a η1flh of 0.75, which was highly practical.

Example 4 2.2-bis (4-nitrophenoxyphenyl/I/)
Bis(4
-Nitrophenoquine (N) sulfone 49.3g (0
, 1 mol) was carried out in the same manner as in Example 3, and a highly practical polymer with ηinh of 0.67 was obtained.

Comparative Example 3 The same operations as in Example 3 were performed except for omitting the dehydration operation, and the obtained polymer had ηinh of 0.21.
This was extremely low.

Example 5 A glass autoclave with an internal volume of 11 was charged with 4,4'-dinitrobenzamide (U, tmo/I/), 0.7 g of Raney nickel aqueous paste, and 300 m7 of 1,3-dimethyl-2-imidazolidinone. After the air in the autoclave was replaced with nitrogen, it was pressurized with hydrogen to 8 kg/cm2 gauge via an intermediate tank of 204.20 kg/m2 gauge. Next, heat to 80℃ while stirring gently.
Subsequently, the reaction was started with vigorous stirring. After that, 90
The temperature was raised to .degree. C., and a hydrogen pressure of 8 kg/am" gauge was continued to be applied inside the autoclave.

Approximately 4 hours after the start of strong stirring, the gauge pressure in the intermediate tank almost stopped decreasing, so stirring was continued for 2 hours to complete the reaction.

Next, the contents were passed through a suction port to remove Raney nickel and other insoluble matter, and the resulting filtration mother liquor was transferred to a flask 11 equipped with a rectification tube and stirrer, 7100 ml of Kishi V was added, and a water stream was added. Aspirate! The water in the system was azeotropically distilled off with xylene by heating under a reduced pressure of -. Subsequently, 100 mJ of xylene was further added, and finally substantially all of the xylene was distilled off to complete the dehydration operation.

When the water content in the obtained dehydrated liquid was measured by the Karl Fischer method, it was found to be 5501) f) m.
, 4'-diaminobenzanilide Analyzed by liquid chromatography and diazo method, purity 99.0%, yield 99.5%
Met.

Next, 32.2 g (0,1-f, ρ) of the above 4,4'-diaminobenzaniliderponic dianhydride was added at a rate such that the internal temperature did not exceed 30°C, and then for 1 hour. Stirring was continued to obtain a polymer stock solution.

Next, this polymer stock solution was poured into water lOβ under strong stirring to precipitate the polymer, which was then washed with water, dehydrated, and dried by heating to obtain a polyimide polymer powder. The obtained polymer has ηinh of 0
．． 71, which was highly practical.

Comparative Example 4 The same operations as in Example 5 were performed except for omitting the dehydration operation, and the obtained polymer had ηinh of 0.31.
This was extremely low.

Comparative Example 5 300 mJ of 1,3-dimethyl-2-imidazolidinone as a solvent? The same procedure as in Example 5 was carried out except that 3 oomg of methyl cellosolve was used instead of xylene and benzene was used instead of xylene as a dehydration aid. Coalescence precipitated, making it impossible to carry out a smooth polymerization operation.

<Effects of the Invention> By implementing the present invention, there is no need to handle aromatic diamine in powder form during the process of synthesizing heat-resistant polymers using aromatic diamine, and the working environment is significantly improved.

Furthermore, since the process for producing aromatic diamine itself is simplified, a significant reduction in the production cost of aromatic diamine is expected.

Patent Applicant Toshi Co., Ltd. Company Procedures
Amendment Document Patent Application No. 223638 of 1985 2, Name of the invention Aromatic polyamic acid and/or manufacturing method of aromatic polyamide (after amendment) 5 Relationship with the case of the person making the amendment Address of the patentee Tokyo Chuo-ku Nihon M Muromachi 2-2 address name
Name Q15)) lj Co., Ltd. voluntarily corrected the entire text as per the appendix. Description 1. Name of ``YJA Group Polyamide Q'2 and/or Process for Producing Aromatic Polyamide 2'', Claim i17 Synthesis Reaction Inhibition. It was prepared by reducing the aromatic dinitro compound or aromatic mononitro amino compound to the lower left of the heterogeneous hydrogenation catalyst in a pure amide polar solvent, and then removing the by-product water by distillation. Double with aromatic diamine solution! A method for producing an aromatic compound, which comprises reacting an aromatic dicarboxylic acid dichloride in an amide group polar solvent.

5. Detailed Description of the Invention <Industrial Application Field> The present invention is directed to the production of aromatic polyamic acid and/or aromatic diamines by directly applying a solution of aromatic diamines obtained from a hydrogenation reaction step to a polymerization step. The present invention relates to a method for producing a group polyamide.

BACKGROUND ART Aromatic diamines have been widely put into practical use as essential components for the production of heat-resistant polymers. Recently, the need for high-performance polymers has been rapidly increasing in the field of advanced industrial technology.
The wings are played by various heat-resistant polymer groups. In that sense, the aromatic diamine industry (Kokeru!
The requirements are increasing even further.

The heat-resistant polymer term is generally a mixture of aromatic diamines and a difunctional aromatic acidic compound, such as bilomeric diamines, at room temperature in an amide polar solvent under anhydrous conditions.
No water 4 course, a water trime
It is synthesized by reacting linotic acid monochloride, terephthal dichloride, isophthal dichloride, etc.

Traditionally, aromatic diamines have been produced by catalytic hydrogen reduction of aromatic dinitro compounds in polar solvents, followed by heating/hot filtration, concentration as necessary, and crystallization to form a single product. It has been done. For example, British Patents 1 and 2
28,738, JP-A-56-22,752, JP-A-57-176.935, etc.

Industrially, aromatic diamines have been supplied in the form of dry powder or flakes.

<Problem to be solved by the invention> However, since aromatic diamines are generally mutagenic IJA (I!E) substances, special environmental measures are required when handling them. It is.

However, since it is handled in the form of powder or flakes, it inevitably generates fine dust, which naturally limits environmental measures. The solution for users of aromatic diamines is to have aromatic diamine manufacturers dissolve aromatic diamines in polymerization solvents and obtain aromatic diamines as a solution. However, as long as aromatic diamine manufacturers handle aromatic diamines in a simple manner, this method simply shifts the dust handling work from the user side to the manufacturer side, and does not provide a fundamental solution. It is clear that this should not be the case.

Therefore, the present inventors conducted extensive studies aimed at utilizing aromatic diamine directly in the polymerization process without isolating it from the aromatic diamine manufacturing process, and as a result, they arrived at the present invention.

Means for Solving the Problems> That is, the present invention provides the following: Aromatic tricarboxylic acid anhydride monochloride and/or O represented by aromatic diamine solution produced by distilling off by-product water after catalytic reduction and/or O general formula CI C-Ar'-CCI (Ar ' indicates a divalent aromatic residue) is reacted with an aromatic dicarboxylic acid dichloride in an amide polar solvent. It is something.

The amide-based polar solvent used in the present invention is a polar solvent that does not exhibit the property of inhibiting the combination reaction between the aromatic diamine compound and the bifunctional aromatic acidic substance and has an amide bond in the molecule, For example, N,N-dimethylacetamide, N·N-diethylacetamide, N-methylpyrrolidone, N-ethylpyrrolidone, N-butylpyrrolidone, N-cyclohexylpyrrolidone, N-methylpiperidone, 1,3-dimethyl-2- Examples include imidazolidinone and hexamethylphosphoramide. Particularly useful are N-methylpyrrolidone and N,N-dimethylacetamide. In addition, N,N-dimethylformamide, which is a similar compound, has an inhibitory effect on the polymerization of the present invention.
It cannot be used for the purpose of this invention.

The aromatic dinitro compound or aromatic mononitroamino compound used in this study has the general formula 02N-Ar"-NO
2 or 02N-Ar''-NH2te, where Ar''- represents a divalent aromatic residue selected from the general formula. Here, R1 is an alkyl group or alkoxy group having 1 to 4 carbon atoms, and X is a direct bond -〇-1-S
-1-C-1-SO2-1 CHICF3 or an integer of 1 to 4; b represents O or an integer of 1 to 12; Specific examples of -A rI+- are as follows.

i.e. (n0(xyoo- -Q-Q-<nO(y etc.

The heterogeneous hydrogenation catalyst used in the present invention is a metal or metal oxide catalyst generally used for catalyzed reduction,
For example, platinum, palladium, rhodium, ruthenium,
Examples include nickel, cobalt, copper, platinum, palladium oxide, and rhodium oxide. Although these metal catalysts can be used in the metal state, they are usually used by being attached to the surface of a carrier such as carbon, barium sulfate, silica gel, or alumina, or Raney catalysts such as nickel, cobalt, or It is also used as The catalyst user should add gold A to 100 parts of the raw material nitro compound, 1U.
The amount is preferably 0.1-10 parts, and preferably 0.1-5 parts when attached to a carrier.

The reaction temperature is generally 20-200℃ (although not limited to this)
A range of 50-130°C is preferred.

Furthermore, the pressure of hydrogen used in the reaction is usually 0.00 gauge pressure.
1 to 50#/d, and the optimum range differs depending on the activity E of the catalyst. For example, in the case of 5% palladium/live carbon and 5% platinum/live carbon, a gauge pressure of 0.1 to 5 kq/d is appropriate, while in the case of Raney nickel, a range of 10 to 50 kg/d is appropriate.

In the hydrogenation reaction of the present invention, -N(J2 +3H2→N
1 mol of N2 by the reaction of 1'12+ 2hiztJ
Two moles of water are extracted from the liquid.

In the present invention, instead of performing a water-cooled reaction, water as a low-boiling component is distilled by heating the mother liquor containing the insoluble catalyst or after recovering the insoluble catalyst by filtration at normal pressure or reduced pressure for 1'-t. Let it come out. At that time, it may be azeotropically distilled off with the solvent in the form of simple distillation, or it may be purified through a rectification column. It is also effective to use an effective azeotropic aid such as benzene, toluene, quinolene, chlorobenzene, etc. in combination. If the internal liquid layer becomes insufficient during the water distillation process, add a solvent and/or a co-containing agent from the outside,
The distillation operation is continued until the water content in the mother liquor becomes 4% I M ', preferably 0.5 %, more preferably 0.1 % or less. After completion of distillation and removal of by-product water, if necessary, insoluble matter is temporarily removed to finally obtain an aromatic diamine solution suitable for polymerization. If the water content in this solution is 1% or more, the reaction rate when reacted with trifunctional or raw aromatic components is extremely low and is not practical.

Ar in the aromatic tricarboxylic anhydride monochloride is a trifunctional aromatic residue in which two of the three functional groups are bonded to adjacent carbon atoms, and O Ar'-CCI Ar' in the aromatic dicarboxylic acid dichloride is a difunctional aromatic residue, for example, is also recommended.

The combination reaction of the present invention is usually carried out using 1 cup of cold solution. A specific example is as follows. That is, an aromatic tricarboxylic acid anhydride monochloride and/or an aromatic tricarboxylic acid anhydride monochloride and/or an aromatic tricarboxylic acid anhydride monochloride and/or an aromatic diamine solution produced by the method of the present invention are added in a substantially equimolar amount (0.9 to L1 times mole) to the aromatic diamine. Gradually add dicarboxylic acid dichloride to
The reaction is carried out at a temperature of 0 to 80°C. Subsequently, if necessary, a hydrogen chloride scavenger in an amount of 0.9 to 1.2 times the amount of acid chloride group is added to obtain a solution of aromatic polyamic acid and/or aromatic polyamide with a high degree of polymerization.

The aromatic polyamide acid obtained here is then subjected to a dehydration ring closure step to be converted into aromatic polyamideimide. The dehydration ring closure operation is carried out either by liquid phase ring closure in solution or solid phase thermal ring closure by heating in a solid. There are two types of liquid phase ring closure: a liquid phase chemical ring closure method using a chemical dehydrating agent, and a simple liquid phase thermal ring closure method. The chemical ring closure method uses aliphatic anhydrides such as acetic anhydride and propionic anhydride at a temperature of 0 to 1.
It is heated at 20°C, preferably 10-60°C. Also,
In the liquid phase thermal ring closure method, a polyamic acid solution is heated at 50 to 400°C.
It is preferably carried out by heating to 100 to 250°C. In this case, it is more effective to use an azeotropic solvent useful for removing water, such as benzene, toluene, xylene, chlorobenzene, etc. in combination. Solid phase thermal ring closure is carried out at 100 to 350°C, preferably 150 to 300°C, in the solid state after converting the polyamic acid polymer from the polyamic acid solution.
This is done by heat treatment at a temperature of ℃.

<Example> Hereinafter, the present invention will be explained in detail using Examples.

Example 1 In a glass autoclave with an internal volume of 11, 4°4'-dinitrodiphenyl ether 26y (0, t mol), 0.82% platinum carbon powder manufactured by Engelhard Japan, and N
- Prepare 300 ml of methyl-2-pyrrolidone, replace the air in the autoclave with nitrogen, and then add 201 ml of hydrogen with hydrogen.
．． 3 via a 20 kq/c4 gauge intermediate tank
It was pressurized to kg/d gauge. Next, the mixture was heated to 90° C. over 30 minutes with gentle stirring, and then the reaction was started with vigorous stirring. Thereafter, a cumulative water pressure of 3 kq/d gauge was continued to be applied inside the autoclave. Approximately 30 minutes after the start of strong stirring, the gauge pressure in the intermediate tank stopped decreasing, and the reaction was then continued for 1 hour to complete the reaction. Next, the contents were passed through a suction port to remove platinum-carbon powder and other insoluble matter, and the obtained filtration mother liquor was transferred to a 16 flask equipped with a rectification tube, a nitrogen gas introduction tube, and a stirrer. Add 100 g of toluene while flowing nitrogen gas to about 120 ~
It was heated to 130° C., and water in the system was azeotropically distilled together with toluene. Subsequently, 100 m/m of toluene was added, and finally substantially all of the toluene was distilled off to complete the dehydration operation.

The water content in the obtained dehydrated liquid was measured by the Karl Fischer method and was found to be 350 p.
- Diaminodiphenyl ether prepared by liquid chromatography and di-r
Purity 99.5%, yield 99.8% when analyzed by l method
It turned out to be.

Next, the 4,4'-diaminodiphenyl ether solution obtained above is mixed with metaphenin/diamine 4.329 (
0.04 mol) of solid powdered trimellitic anhydride monochloride 2 while stirring.
9.5 y (0.14 mol) at an internal temperature of 30℃
The mixture was added at a rate not exceeding 100 ml, and stirring was continued for 1 hour to obtain a polyamic acid polymer, Ikkyo liquid. Next, mix this polymer stock solution with water under strong stirring! 01 to precipitate the polymer, followed by water washing/dehydration/drying/heat treatment to obtain a polyamideimide polymer powder. Logarithmic viscosity η1n of the obtained polymer
h (0 degrees: U, 5 y/dl, H8 medium: N-Mef
k-2-pyrrolidone (temperature: 30°C) was measured and found to be 0.82, which is highly practical.

Comparison vlJl The same operations as in Example 1 were performed except that the dehydration operation was omitted, and the obtained polymer had ηinh of 0.2.
It was extremely low at 9.

Comparative Example 2 The same operation as in Example 1 was performed except that 300 ml of N·N-dimethylformamide was used instead of 300 ml of reaction solvent N-methyl-2-pyrrolidone, and the obtained polymer had ηinh of 0.25. This was extremely low.

Example 2 4,4'-dinitrodiphenyl ether 26f(0,
The same procedure as in Example 1 was carried out except that 4-nitro-3'-aminodiphenyl ether 23F (0.1 mol) was used instead of 1 mol), and ηinh was 0.
．． A highly practical polymer named No. 86 was obtained.

Example 3 A 2° 2-bis(
4-Nitrophenoxyphenyl)propane 47.1 F (0.1 mol), Nippon Engel Nord Co., Ltd. 5, palladium-carbon powder 2y, and Hedimethylacetamide 400ml were charged, and the air in the autoclave was replaced with nitrogen. After that, water tower 201.2
0 *2 kq via q/ci gauge intermediate tank
/c-gauge was pressurized. Next, the mixture was heated to 80° C. while stirring gently for 17 minutes, and the reaction was then started with vigorous stirring. Thereafter, a hydrogen pressure of 2 kg/d gauge was applied inside the autoclave. About 3 hours after the start of strong stirring, the gauge pressure in the intermediate tank almost stopped decreasing, so stirring was continued for 2 hours to complete the reaction. Next, the contents were passed through a suction port to remove palladium-carbon powder and other insoluble matter, and the resulting filtration mother liquor was transferred to a 11 flask equipped with a rectifier, a nitrogen gas inlet tube, and a stirrer. 100 tons of monochlorobenzene was heated to about 140 to 150° C. for 2 days while supplying gas, and the water in the system was distilled out together with the monochloropenze. Subsequently, monochlorobenzene+00w1 was further added, and finally, virtually all of the monochlorobenzene was removed, and the dehydration operation was completed.

The water content in the obtained dehydrated liquid was measured using the Karl Fischer method and found to be 2301? l, and also generated 2, 2
-Bis(4-aminophenoxyphenyl)propane was analyzed by liquid chromatography and diazo method and found to be 99.1% pure.
, yield was 99.9%.

Next, the flask containing the above 2,2-bis(4-aminophenoxyphenyl)propane solution was placed in an ice-water bath, and while stirring, a mixture of solid powder of terephthalic acid dichloride/isophthalic acid dichloride (1/1 molar ratio) 20. 3 f
(0.1 mol) was added at such a rate that the internal temperature did not reach 30°C, and stirring was continued for 1 hour! 1
(A stock solution of coalescence was obtained. Next, this polymer) Keisei was poured into water 101 under strong stirring to precipitate the polymer, which was washed with water/dehydrated/heated and dried to obtain a polyamide polymer powder. The obtained polymer had a ηinh of 0.75, which was insufficient for practical use.

Example 4 Bis(4
-nitrophenoxyphenyl)sulfone (0.1 mol)
When the same operations as in Example 3 were performed except for using , a highly practical polymer with ηinh of 0.67 was obtained.

Comparative Example 3 The same operations as in Example 3 were performed except for omitting the dehydration operation, and the obtained polymer had ηinh of 0.21.
This was extremely low.

Example 5 In a glass autoclave with an internal volume of 11, 4.4'-dinitrobenzamide ranee nickel aqueous paste 0.7 f L and 3-
Prepare 300ml of dimethyl-2-imidazolidinone,
After replacing the air in the autoclave with nitrogen, mizuna
It was pressurized to 8 y/d gauge via an intermediate tank of 0 l 120 #/d gauge. Next, the mixture was heated to 80° C. with gentle stirring, and then the reaction was started with vigorous stirring. Thereafter, the temperature was raised to 90°C, and a cumulative water pressure of 8 kg/c4 gauge was continued to be applied inside the autoclave. Approximately 4 hours after the start of strong stirring, the gauge pressure in the intermediate tank almost stopped decreasing, so stirring was continued for 2 hours to complete the reaction.

Next, the contents were passed through a suction port to remove Raney nickel and other insoluble matter, and the obtained filtration mother liquor was transferred to a 11 flask equipped with a fine detonator and a stirrer, and 100 m/m of xylene was added thereto, and a water-jet aspirator was added. The water in the system was azeotropically distilled off along with xylem by heating under the pressure of . Next is xylene! 00 ml was further added, and finally substantially all of the xylene was distilled off to complete the dehydration operation. The water content in the obtained dehydrated liquid was measured by the Karl Fischer method and found to be 550.
The resulting 4,4'-diaminobenzanilide was analyzed by liquid chromatography and diazo method and found to have a purity of 99.0% and a yield of 99.5%.

Next, the flask containing the above 4,4'-diaminobenzanilide solution was placed in an ice-water bath, and while stirring, solid powdered trimellitic anhydride monochloride 21.11 (0,
1 mol) was added at a rate such that the internal temperature did not exceed 30°C, and stirring was continued for 1 hour to obtain a polyamide di coalescence stock solution. Next, add this polymer stock solution to 10 ml of water under strong stirring.
The polymer was precipitated by water washing/dehydration/drying/heat treatment to obtain a polyamideimide polymer powder.

The obtained polymer had a ηinh of 0.59, which was highly practical.

Comparative Example 4 All operations were performed in the same manner as in Example 5 except that the dehydration operation was omitted.
It was extremely low at 8.

Comparative Example 5 The same procedure as in Example 5 except that 300 ml of methyl cellosolve was used instead of 300 gt of 1,3-dimethyl-2-imidazolidinone as a solvent, and benzene was used instead of xylene as a dehydration aid. When this process was carried out, partially bonded low polymers precipitated during the latter half of the polymerization process, making it impossible to carry out the polymerization process smoothly.

<Effects of the Invention> By carrying out the present invention, there is no need to handle aromatic diamine in powder form during the process of synthesizing aromatic polyamic acid and/or aromatic polyamide using aromatic diamine, and the work environment is improved. Significantly improved.

Furthermore, since the process for producing aromatic diamine itself is simplified, a significant reduction in the production cost of aromatic diamine and, in turn, of aromatic polyamic acid and/or aromatic polyamide is expected.

Claims (1)

[Claims] It is characterized by catalytically reducing an aromatic dinitro compound or an aromatic mononitroamino compound in an amide polar solvent that does not inhibit the polymerization reaction in the presence of a heterogeneous hydrogenation catalyst, and then removing by-product water by distillation. A method for producing an aromatic diamine solution for polymerization.