JP3386383B2 - Method for producing polyimide - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing a polyimide by a one-step method using a specific catalyst.

[0002]

2. Description of the Related Art Polyimide is a material expected to be used in various fields requiring heat resistance because it is excellent in workability, electrical insulation, mechanical strength and the like. Conventionally, polyimide is
It has been produced by a method in which a tetracarboxylic acid anhydride and a diamine are reacted to form a precursor polyamic acid, which is heated and dehydrated at a high temperature for a long time and cyclized. But,
Polyamic acid is unstable and easily hydrolyzes with water,
It had the drawback of poor storage stability. So far
A method using acetic anhydride and triethylamine, pyridine and acetic anhydride, or pyridine and triphenyl phosphite as catalysts for producing polyimide from polyamic acid has been proposed, but it was not a practical method. Further, in the method for producing a polyimide by the one-step method, a composite catalyst is used,
Only a method of reacting at a high temperature of 60 to 180 ° C. has been proposed.

[0003]

It is an object of the present invention to improve the above method and establish a practical method for producing a polyimide in one step.

[0004]

The method of the present invention comprises a tetracarboxylic anhydride and a diamine in a molar ratio of 1 to 0.5:
9,10-dihydro-9-oxa- of the following formula I as a catalyst in a solvent in an inert gas stream in a ratio of 0.5 to 1
It is a method for producing a polyimide, which is reacted in the presence of 10-phosphaphenanthrene-10-oxide.

[0005]

[Chemical 1]

An example of the method for producing the polyimide of the present invention is shown by the reaction formula as follows.

[0007]

[Chemical 2]

The catalyst can be subjected to a dehydration ring closure reaction in the presence of 0.2 to 10% by weight. Reaction temperature is 1
It can be performed at 30 to 160 ° C. As the inert gas used in the present invention, nitrogen gas, argon gas and the like are suitable.

The solvent has a solubility parameter of 8.5.
~ 9.5 aromatic solvent and solubility parameter 9.0-1
After using the polar solvent of 2.1 as a mixed solvent of 30 to 70% by weight: 70 to 30% by weight for dehydration reaction and confirming that water necessary for producing a corresponding polyimide was distilled out. A branched or straight chain alcohol having 1 to 4 carbon atoms,
The corresponding polyimide can be obtained by precipitating the polyimide in a poor solvent such as hydrous alcohol or in water, filtering, washing again with a poor solvent if necessary, filtering, and drying at 80 to 150 ° C. Examples of the aromatic solvent having a solubility parameter of 8.5 to 9.5 include toluene, xylene, ethylbenzene, chlorobenzene, and the like, which may be used alone or in combination. Examples of the polar solvent having a solubility parameter of 9.0 to 12.1 include dimethylacetamide, diethylacetamide, dimethylformamide, diethylformamide, isophorone, N-methylpyrrolidone and the like, which may be used alone or in combination. it can.

The tetracarboxylic acid anhydride used in the present invention is an aromatic, alicyclic or aliphatic tetracarboxylic acid anhydride having 4 to 39 carbon atoms. For example, the following may be used alone or in combination of two or more. It can be mixed and used. Pyromellitic anhydride, diphenyl ether tetracarboxylic acid anhydride, benzophenone tetracarboxylic acid anhydride, maleated cyclohexene tetracarboxylic acid anhydride, cyclobutane tetracarboxylic acid dianhydride, 3,3 ′, 4,4′-biphenyl tetracarboxylic acid Dianhydride, 4,4 '-(1,
4-phenylenedioxy) phthalic anhydride, 2,2-
Bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, tetralin dianhydride, perylene tetracarboxy dianhydride, 1,4-difluoro-
2,3,5,6-benzenetetracarboxylic dianhydride,
2,3,5-Tricarboxycyclopentylacetic acid dianhydride, bicyclo (2,2,1) heptanetetracarboxylic dianhydride, bicyclo (2,2,2) oct-7-ene-
2,3,5,6-tetracarboxylic dianhydride, butanetetracarboxylic dianhydride, diphenylsulfonetetracarboxylic dianhydride.

The diamine used in the present invention has 4 to 4 carbon atoms.
39 aromatic, alicyclic or aliphatic amines. Examples of these diamines include the following alone or
The above can be mixed and used. 2,2-bis [4- (4-aminophenoxy) phenyl] propane,
Diaminodiphenyl sulfone, o-tolidine, 4,4 '
-Methylenedianiline, diaminodicyclohexylmethane, 4,4'-diaminodiphenyl ether, 3
(4), 8 (9) -bis (aminomethyl) tricyclo-
[5,2,1,0 ^2.6] decane, 2,4-toluenediamine, 1,3-bis (4-aminophenoxy) benzene, bis [4- (4-aminophenoxy) phenyl] sulfone, Tetoradein, 4,4'-methylene-bis (2
-Chloroaniline), 3,3'-diaminobenzophenone, bisaminopropylpolydimethylsiloxane, 2,
2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl, 2,2'-bis [4- (4-amino Phenoxy) phenyl] hexafluoropropane, 2,7-diamino-9-fluorene, 1,
10-diaminodecane, 9,9-bis (4-aminophenyl) fluorene.

[0012]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. Example 1 41 g of 2,2′-bis [4- (4-aminophenoxy) phenyl] propane in a reaction flask equipped with a cooling condenser equipped with a test tube, a thermometer, a stirrer, a dropping funnel, and a gas blowing tube, 2.5 g of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and 260 g of xylene were added, and nitrogen gas was introduced through a gas blowing tube and stirred. Next, 31 g of o-diphenyl ether tetracarboxylic acid anhydride dissolved in 240 g of dimethylacetamide was added dropwise at 10 to 30 ° C. The reaction was carried out at 130 to 150 ° C. for 3 hours, and 3.62 g of water produced (calculated value 3.6 g) was removed from the test tube. The reaction product obtained by collecting and removing 250 g of the solvent was poured into 500 g of methanol, the solid matter was separated by filtration, washed with 250 g of methanol, and then dried under reduced pressure at 80 to 130 ° C. Yield 67.4 g (yield 98.5%), intrinsic viscosity ηi
nh (0.5g / dl DMAC30 ° C) 0.68dl / g, decomposition temperature 548 ° C (Air).

Example 2 A device similar to that of Example 1 except that 20 g of 4,4'-diaminodiphenyl ether and 120 g of o-xylene were added, nitrogen gas was passed through, and pyromellitic anhydride 21.8 was introduced.
g dissolved in 100 g of dimethylformamide,
Added at 20-40 ° C. With this 9,10-dihydro-9
-Oxa-10-phosphaphenanthrene-10-oxide (0.84 g) was added, and the mixture was reacted at 135 to 140 ° C for 3.5 hours to produce water (3.61 g, calculated amount: 3.6 g).
Was removed from the test tube. The reaction product was cooled to 10 ° C. and the crystalline substance was filtered off. After washing the crystals with 100 g of methanol,
It was dried with hot air at 135 ° C. Yield 37.8 g (yield 99
%), Decomposition temperature 559 ° C. (Air). Compared with the conventional two-step method using polyamic acid, the low temperature (135-148
A polyimide could be obtained at (.degree. C.).

Example 3 A device similar to that of Example 1 was charged with 17.9 g of diphenylsulfone tetracarboxylic acid dianhydride, 120 g of xylene and 110 g of dimethylacetamide, and nitrogen gas was introduced thereinto to obtain 2,2'-bis [ After 20.5 g of 4- (4-aminophenoxy) phenyl] propane was added portionwise at 20 to 40 ° C., 1.15 g of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide was added. In addition, the reaction was carried out at 140 to 148 ° C. for 3 hours to obtain 1.8
5 g (calculated value 1.8 g) was separated. After distilling off 70 g of the solvent, it was poured into 300 g of methanol. The solid matter was filtered off, washed again with 100 g of methanol, and the separated powder was dried at 80 ° C. for 1 hour and 140 ° C. for 5 hours. Yield 3
5.9 g (yield 98%), ηinh (0.5 g / dl DMA
C 30 ° C.) 0.51 dl / g, decomposition temperature 527 ° C. (Air).

Example 4 In a device similar to that of Example 1, 19.4 g of the following diamine and 150 g of monochlorobenzene were introduced, and nitrogen gas was introduced, and 31 g of diphenyl ether tetracarboxylic acid anhydride was dissolved in 120 g of dimethylacetamide. Was added at 20-40 ° C.

[0016]

[Chemical 3]

To this, 9,10-dihydro-9-oxa-
10-phosphaphenanthrene-10-oxide 2 g
Was added and the mixture was reacted at 140 to 150 ° C. for 3.5 hours to remove 3.63 g (calculated value 3.6 g) of produced water. After removing 90 g of the solvent from the reaction system, methanol 500
The solid component was separated into solids which had been washed with 200 g of methanol and dried at 80 ° C. for 1 hour and 140 ° C. for 5 hours. Yield 45.4 g (97% yield), ηinh
(0.5 g / dl DMAC 30 ° C) 0.32, decomposition temperature 477 ° C (Air).

Example 5 To 22.2 g of 4,4'-hexafluoroisopropylidene diphthalic anhydride, 100 g of xylene and 80 g of dimethylformamide were placed in the same apparatus as in Example 1, and argon gas was introduced. 1,4-Phenylenediamine 5.5
g added at 30-40 ° C., 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-
Oxide (0.55 g) was added, and the mixture was reacted at 135 to 143 ° C. for 4 hours to generate 1.85 g of distilled water (calculated value 1.8).
g) was removed and 80 g of the solvent was removed, cooled to 20 ° C., 300 g of methanol was added, the precipitated solid was filtered off, washed again with 100 g of methanol and filtered,
It was dried at 140 ° C. for 5 hours. Yield 25g (Yield 97
%), Ηinh (0.5 g / dl NMP 30 ° C.) 0.33,
Decomposition temperature 554 ° C (Air).

2,2'-bis [4- (4-aminophenoxy) phenyl] propane 1 was placed in the same apparatus as in Example 1.
6.4 g and xylene 120 g were charged, nitrogen gas was introduced, and at 20 to 80 ° C., 6.2 g of o-diphenyl ether tetracarboxylic acid anhydride was added to dimethylacetamide 80.
After adding the one dissolved in g, 9,10-dihydro-9
-Oxa-10-phosphaphenanthrene-10-oxide (0.6 g) was added, and the mixture was reacted at 140 to 145 ° C for 3 hours to remove water (0.74 g) (calculated value 0.72 g). I left. The reaction product was cooled to 20 ° C., added to 200 ml of methanol, the crystallized product was filtered off, washed with 50 ml of methanol and filtered off, and dried at 80 ° C. for 2 hours and at 130 ° C. for 3 hours. Yield 21.1 g (yield 96.4%), amine value 102.21 (calculated value 102.21).
56).

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Keizo Tsukamoto               92 Manooki-cho, Fukuyama-shi, Hiroshima Manac stock               Ceremony company Minohoki factory (72) Inventor Masaru Mori               92 Manooki-cho, Fukuyama-shi, Hiroshima Manac stock               Ceremony company Minohoki factory                (56) References JP 2001-213961 (JP, A)

Claims (5)

(57) [Claims] 1. A tetracarboxylic acid anhydride and a diamine,
At a molar ratio of 1 to 0.5: 0.5 to 9,10-dihydro-9-oxa-1 in a solvent in an inert gas stream.
A method for producing a polyimide, which comprises reacting in the presence of 0-phosphaphenanthrene-10-oxide. 2. 9,10-Dihydro-9-oxa-10
-Phosphaphenanthrene-10-oxide was added to 0.
The method for producing a polyimide according to claim 1, wherein the reaction is performed in the presence of 2 to 10% by weight. 3. The reaction is carried out with a solubility parameter of 8.5-
9.5 aromatic solvents and solubility parameters 9.0-1
The method for producing a polyimide according to claim 1, which is carried out in a mixed solution of the polar solvent of 2.1. 4. The method for producing a polyimide according to claim 1, wherein the reaction is performed at a temperature of 130 to 160 ° C. 5. In the solvent according to claim 3, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-1.
A method for producing a polyimide, comprising a step of dehydrating a polyamic acid in the presence of 0-oxide.