JPH08120080A - Polyamic acid and production of polymer from polyamic acid through ring closure by dehydration - Google Patents

Abstract

PURPOSE: To obtain a high-mol. polyamic acid which gives a coating film reduced in cracking by reacting a tetracarboxylic dianhydride with a diamine in the presence of a compound containing one carboxyl group per molecule. CONSTITUTION: A tetracarboxylic dianhydride (A) is reacted with a diamine (B) (e.g. p-phenylenediamine) in the presence of a compound (C) containing one carboxyl group per molecule to produce a polyamic acid. This acid is caused to undergo ring closure by dehydration to produce a polymer. Preferred examples of the ingredient (A) include butanetetracarboxylic dianhydride and 1,2,3,4-cyclobutanetetracarboxylic dianhydride. Examples of the ingredient (C) include acetic acid and benzoic acid. The obtained polyamic acid and its polymer are useful as a liquid-crystal alignment film, an insulating film for a semiconductor circuit element, a covering material for an enameled wire, an adhesive, a coating compound, etc.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a high molecular weight polyamic acid and a process for producing a high molecular weight polymer obtained by dehydration ring closure of the polyamic acid.

[0002]

2. Description of the Prior Art Generally, polyimide has excellent heat resistance and is therefore very useful as a raw material for films or electric wire coating materials, adhesives, paints, etc., which are used at high temperatures. The polyimide film or coating is obtained by polymerizing a tetracarboxylic dianhydride and a diamine in a polar solvent to obtain a polyamic acid, and then applying a solution of the polyamic acid to a substrate and drying it, followed by dehydration by a method such as heating. It can be obtained by ring closure.

The film or coating obtained by such a method has a drawback that cracks are generated and mechanical strength is inferior. The drawback is that the molecular weight of the polyamic acid is low and the molecular weight of the polyimide derived from the polyamic acid is low. Is low.

[0004]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a high molecular weight polyamic acid and a process for producing a high molecular weight polymer by dehydration ring closure of the polyamic acid.

[0005]

According to the present invention, a first
In addition, tetracarboxylic dianhydride (hereinafter referred to as "compound A") and diamine (hereinafter referred to as "compound B"), the presence of a compound containing one carboxyl group in the molecule (hereinafter referred to as "compound C") There is provided a method for producing a polyamic acid, which comprises reacting below.
Further, there is provided a method for producing a ring-closing polymer of polyamic acid (hereinafter, referred to as "polymer (A)), which comprises dehydrating and ring-closing the polyamic acid produced by the above-mentioned production method, and the method according to the present invention as set forth above. The purpose is achieved.

Hereinafter, the present invention will be described in detail, by which the purpose, constitution, effect and advantage of the present invention will become apparent.

Method for producing polyamic acid Compound A, which is a tetracarboxylic dianhydride used for producing polyamic acid, has the following formula (1):

[0008]

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A compound represented by the formula (1), wherein R ¹ is a tetravalent organic group.

Examples of the tetravalent organic group R ¹ in the above formula (1) include an aliphatic group, an aromatic group and an alicyclic group. Further, the carbon number of R ¹ is preferably 4 to 14. Specifically, the following formulas (2-1) to (2-1)
1)

[0011]

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(In the formula, R ^{2 to} R ⁵ are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and a, b and c are each independently an integer of 0 or 1.)

[0013]

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(In the formula (2-5), R ⁶ is an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, or a halogen atom, and d is an integer of 0 to 4.)

[0015]

[Chemical 4]

(In the formula (2-6), R ⁷ is an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms or a halogen atom, and e is an integer of 0 to 2.)

[0017]

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(In the formula (2-9), R ⁸ is an oxygen atom, an alkylene group having 2 to 14 carbon atoms, a methylene group, and 2 to 5 carbon atoms.
Is an alkylidene group, a halogenated alkylidene group having 2 to 5 carbon atoms, a halogenated alkylene group having 2 to 5 carbon atoms, a sulfur atom, a sulfone group or a ketone group, and f is an integer of 0 or 1. )

[0019]

[Chemical 6]

A group represented by can be mentioned. Among them, formulas (2-1), (2-2), (2-3) and (2-
Tetravalent groups represented by 5), (2-8) and (2-9) are preferable.

Specific examples of the compound A include, for example, butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride. , 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, tetracyclo [6,
2,1,1,0 ^2,7 ] Dedoca-4,5,9,10-tetracarboxylic dianhydride, 3,5,6-tricarboxynorbornane-2-acetic acid dianhydride, 2,3,4 , 5-Tetrahydrofuran tetracarboxylic dianhydride, 1,3,3a, 4,5,9
b-Hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 5- (2,5-dioxotetrahydrofuryl)- 3-methyl-3-cyclohexene-1,2-
Aliphatic and alicyclic tetracarboxylic dianhydrides such as dicarboxylic dianhydrides, bicyclo [2,2,2] -oct-7-ene-2,3,5,6-tetracarboxylic dianhydrides;

Pyromellitic dianhydride 3,3 ', 4,4'
-Benzophenone tetracarboxylic acid dianhydride 3,3 ',
4,4'-biphenylsulfone tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 3,3 ' , 4,4'-Biphenyl ether tetracarboxylic acid dianhydride, 3,3 ', 4,4'-dimethyldiphenylsilane tetracarboxylic acid dianhydride, 3,3', 4,4'-tetraphenylsilane tetracarboxylic acid Acid dianhydride, 1,2,
3,4-furantetracarboxylic dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenyl sulfone Dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylpropane dianhydride, 3,3 ', 4,4'-perfluoroisopropylidene diphthalic acid dianhydride, 3,3' , 4,4'-biphenyltetracarboxylic dianhydride, bis (phthalic acid) phenylphosphine oxide dianhydride, p-phenylene-
Bis (triphenylphthalic acid) dianhydride, m-phenylene-bis (triphenylphthalic acid) dianhydride, bis (triphenylphthalic acid) -4,4'-diphenylether dianhydride, bis (triphenylphthalic acid) ) -4,4'-Diphenylmethane dianhydride and other aromatic tetracarboxylic dianhydrides can be mentioned.

Of these, butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, tetracyclo [6, 2,1,1,0 ^2,7 ]
Dodeca-4,5,9,10-tetracarboxylic dianhydride,
1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, pyromellitic acid Dianhydride, 3,3 ', 4,4'-benzophenone tetracarboxylic acid dianhydride, 3,3', 4,4'-biphenylsulfone tetracarboxylic acid dianhydride, 3,3 ', 4,4 '-Perfluoroisopropylidene diphthalic acid dianhydride, 3,
3 ', 4,4'-biphenyltetracarboxylic dianhydride and the like are preferable.

These compounds A can be used alone or in combination of two or more.

The diamine reacted with the compound A, that is, the compound B is represented by the following formula (3)

[0026]

[Chemical 7]

(In the formula (2), R _B is a divalent organic group).

Specific examples of R _B which is the divalent organic group are represented by the following formulas (4-1) to (4-8)

[0029]

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(In the formula (4-1), R ⁹ is an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms or a halogen atom, and g is an integer of 0 to 4.)

[0031]

[Chemical 9]

(In the formula (4-2), R ¹⁰ is an oxygen atom, a methylene group, an alkylene group having 2 to 14 carbon atoms, or a 2 to 5 carbon atom.
Alkylidene group, a halogenated alkylidene group having 2 to 5 carbon atoms, a halogenated alkylene group having 2 to 5 carbon atoms, a sulfur atom, a sulfone group, a ketone group and the following formula (4-2
1), (4-2-2) and (4-2-3)

[0033]

[Chemical 10]

Is one of the divalent groups represented by
R ¹¹ and R ¹² are each independently the same as R ⁹ , and h and i are each independently an integer of 0 to 4. )

[0035]

[Chemical 11]

(In the formula (4-3), R ¹³ and R ¹⁴ are each independently the same as R ¹⁰ , and R ¹⁵ , R ¹⁶ and R ^{17 are the same.}
Are each independently the same as R ⁹ above, and include j, k and l
Are each independently an integer of 0 to 4. )

[0037]

[Chemical 12]

(In the formula (4-5), R ¹⁸ and R ¹⁹ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and m is an integer of 1 to 20.)

[0039]

[Chemical 13]

(In the formula (4-6), R ²⁰ , R ²¹ , R ²² and R ²³ are each independently an alkyl group having 1 to 12 carbon atoms, and n and p are each independently 1 to 3 Is an integer of 0
Is an integer of 1 to 20. )

[0041]

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(In the formula (4-7), R ²⁴ is an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms or a halogen atom, and q is an integer of 0 to 4.)

[0043]

[Chemical 15]

(In formula (4-8), R ²⁵ is the same as R ¹⁰ , R ²⁶ and R ^{27 are} independently the same as R ⁹ , and r and s are independently 0 to 0. 4 is an integer of 4.). Among them, 2 represented by the formulas (4-1), (4-2) and (4-3)
Valuable groups are preferred.

Specific examples of the compound B include p-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylethane, 4,4'-diaminodiphenyl sulfide, 4,
4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl ether, 1,5-diaminonaphthalene, 3,
3'-dimethyl-4,4'-diaminobiphenyl, 4,4 '
-Diaminobenzanilide, 3,4'-diaminodiphenyl ether, 3,3'-diaminobenzophenone, 3,4 '
-Diaminobenzophenone, 4,4'-diaminobenzophenone, 2,2-bis [4- (4-aminophenoxy)
Phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,
2-bis (4-aminophenyl) hexafluoropropane, bis [4- (4-aminophenoxy) phenyl] sulfone, 1,4-bis (4-aminophenoxy) benzene, 4,4 ′-(p-phenylenediene Isopropylidene) bisaniline, 4,4 '-(m-phenylenediisopropylidene) bisaniline, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 9,9- Bis (4-aminophenyl)-
10-hydroanthracene, 9,9-bis (4-aminophenyl) fluorene, 4,4'-methylene-bis (2-
Chloroaniline), 2,2 ', 5,5'-tetrachloro-4,
4'-diaminobiphenyl, 2,2'-dichloro-4,4 '
-Diamino-5,5'-dimethoxybiphenyl, 3,3'-
Aromatic diamines such as dimethoxy-4,4'-diaminobiphenyl;

Aromatic diamine having a hetero atom such as diaminotetraphenylthiophene; 1,1-metaxylylenediamine, 1,2-ethylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine , Heptamethylenediamine, octamethylenediamine, nonamethylenediamine, 1,4-diaminocyclohexane, isophoronediamine, tetrahydrodicyclopentadienylenediamine, hexahydro-4,7-methanoindanylene dimethylenediamine, tricyclo [6,2 , 1,0 ^2.7 ] -Undecylenedimethyldiamine, 4,4′-methylenebis (cyclohexylamine) and other aliphatic or alicyclic diamines can be mentioned.

Of these, p-phenylenediamine,
4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 9,9-bis (4-
Aminophenyl) fluorene, 2,2-bis [4- (4
-Aminophenoxy) phenyl] hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, 4,4 '-(p-phenylenediisopropylidene) bisaniline, 4,4'-(m-phenylenediene Isopropylidene) bisaniline and the like are preferable.

These compounds B can be used alone or in combination of two or more kinds.

In the method for producing a polyamic acid of the present invention, when the compound A and the compound B are reacted with each other, the compound C, that is, the compound having one carboxyl group in the molecule is present. As the compound C, the following formula (6)

[0050]

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A compound represented by the formula (6), wherein R _C is a monovalent group, can be mentioned.

R _C in the above formula (6) is a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, for example, 1 to 1 carbon atoms.
2 alkyl groups, 6-12 carbon aromatic groups, 3 carbon atoms
To 12 alicyclic groups and the like.

Further, examples of R _C include a fluorinated hydrocarbon group in which the hydrogen atom of the above hydrocarbon group is substituted with a fluorine atom.

Specific examples of compound C include acetic acid, propionic acid, trifluoroacetic acid, benzoic acid, n-butyric acid, isobutyric acid, n-caproic acid, isocaproic acid, formic acid, cyclopropanecarboxylic acid, cyclobutanecarboxylic acid, cyclobutane. Mention may be made of pentanecarboxylic acid, cyclohexanecarboxylic acid, acrylic acid, methacrylic acid and the like. Of these, acetic acid, propionic acid, trifluoroacetic acid, benzoic acid, n-butyric acid, isobutyric acid, n-caproic acid, isocaproic acid and formic acid are particularly preferable.

When the polyamic acid is produced by reacting the compound A with the compound B, the proportion of the compound C used is preferably 10 to 1000 parts by weight, more preferably 200 to 800 parts by weight, relative to 100 parts by weight of the compound A. It is a department. By using the compound C in the above range, the effect of using the compound C, that is, the effect of stably obtaining a high molecular weight polyamic acid is further excellent.

The reaction of the compound A with the compound B is usually 0 to 150 ° C., preferably 0 to 100 ° C. in the presence of an organic solvent.
At a reaction temperature of 1 to 48 hours.

The organic solvent used in the reaction is not particularly limited as long as it can dissolve the compound A, the compound B, the compound C and the polyamic acid produced in the reaction. For example, aprotic polar solvent such as γ-butyrolactone, N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, tetramethylurea, hexamethylphosphortriamide; m- Phenolic solvents such as cresol, xylenol, phenol and halogenated phenol can be mentioned. The organic solvent is usually such that the total amount of the compound A and the compound B is 0.1 to 3 with respect to the total amount of the reaction solution.
It is preferably used so as to be 0% by weight.

The ratio of the compound A to the compound B used is preferably 0.2 to 2 equivalents of the acid anhydride group of the compound A, more preferably 0 equivalent to 1 equivalent of the amino group in the compound B. 0.3 to 1.4 equivalents.

Method for Producing Polymer (A) The polymer (A) in the present invention is usually polyimide or polyisoimide. The polymer (A) can be obtained by subjecting the above-mentioned polyamic acid to ring closure by dehydration with or without heating, preferably in the presence of a tertiary amine and an acid anhydride.

The reaction temperature in the case of dehydration ring closure by heating only is preferably 60 to 200 ° C., more preferably 10
It is 0 to 170 ° C. The reaction temperature in the case of dehydration ring closure by heating in the presence of a tertiary amine and an acid anhydride is preferably 0 to 180 ° C, more preferably 60 to 150 ° C.
Is.

Examples of the acid anhydride include acetic anhydride,
Propionic anhydride, trifluoroacetic anhydride, etc. can be mentioned. Examples of the tertiary amine include pyridine, collidine, lutidine, triethylamine and the like. The amount of the acid anhydride used is preferably 1.6 to 20 mol per 1 mol of the repeating unit of the polyamic acid. Further, the amount of the tertiary amine used is preferably 0.5 to 10 mol with respect to 1 mol of the acid anhydride used.

[0062]

EXAMPLES The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. The intrinsic viscosity of the polymer is N-methyl-
It is measured at 30 ° C. in 2-pyrrolidone. In the following description of the examples, polyamic acid is abbreviated as polymer D and dehydrated ring-closing polymer is abbreviated as polymer E.

Example 1 24.8 g of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 21.6 g of p-phenylenediamine and 224.0 g of acetic acid (500 to 100 parts by weight of compound A)
(Parts by weight) was dissolved in 988 g of N-methyl-2-pyrrolidone and reacted at room temperature for 6 hours. The reaction mixture was then poured into a large excess of methanol to precipitate the reaction product. After that, it is washed with methanol, and it is dried under reduced pressure at 40 ° C.
After being dried for an hour, polymer D having an intrinsic viscosity of 2.64 dl / g
-1 was obtained in an amount of 60.3 g.

Example 2 30.0 g of the polymer D-1 obtained in Example 1 was dissolved in 570 g of γ-butyrolactone, 21.6 g of pyridine and 16.74 g of acetic anhydride were added, and dehydration was carried out at 120 ° C. for 3 hours. The ring was closed. Then, the reaction product solution was treated in the same manner as in Example 1 to precipitate the product, which was washed and dried to obtain 24.5 g of Polymer E-1 having an intrinsic viscosity of 2.53 dl / g.

Example 3 80.2 g of a polymer D-2 was obtained in the same manner as in Example 1 except that 39.6 g of 4,4'-diaminodiphenylmethane was used as the diamine. D
2-30.0 g was used for dehydration ring closure in the same manner as in Example 2 to obtain 2 parts of polymer E-2 having an intrinsic viscosity of 2.36 dl / g.
2.9 g was obtained.

Example 4 Intrinsic viscosity was 2.58 dl / g in the same manner as in Example 1 except that 39.22 g of cyclobutanetetracarboxylic acid dianhydride was used as the tetracarboxylic acid dianhydride.
51.5 g of polymer D-3 was obtained.

Example 5 In Example 1, tetracarboxylic acid dianhydride was added to 1,3,
3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-
c] 77.5 g of polymer D-4 was obtained in the same manner as in Example 1 except that 60.0 g of furan-1,3-dione was used, and 30.0 g of this polymer D-4 was used in Example 2 The dehydration ring closure was carried out in the same manner as above to obtain 23.2 g of polymer E-4 having an intrinsic viscosity of 2.39 dl / g.

Example 6 Polymer D having an intrinsic viscosity of 2.76 dl / g was prepared in the same manner as in Example 1 except that 43.6 g of pyromellitic dianhydride was used as the tetracarboxylic dianhydride. 50.7 g of -5 was obtained.

Examples 7 to 18 In Example 1, polymer D was synthesized by changing the kind and addition amount of compound C as shown in Table 1. Polymer D obtained
Intrinsic viscosity was measured and is shown in Table 1 together with the results of Examples 1 to 6 and Comparative Example 1 described later.

Comparative Example 1 When the reaction was carried out in Example 1 without adding acetic acid and the same operation as in Example 1 was carried out, the intrinsic viscosity of the polymer D was as low as 1.44 dl / g. .

[0071]

[Table 1]

[0072]

The polyamic acid and its dehydrated ring-closure polymer obtained by the production method of the present invention have a high molecular weight, and therefore, when formed into a coating film, few cracks are generated and the mechanical strength is excellent. Therefore, it is useful for, for example, high temperature films, adhesives, paints, and the like, and specifically for printed wiring boards, insulating films for semiconductor integrated circuit devices, liquid crystal alignment films, coating materials for enamel electric wires, various laminated plates, gaskets, etc. It is useful.

Preferred embodiments of the method for producing a polyamic acid and the method for producing a dehydrated ring-closing polymer of a polyamic acid according to the present invention, which have been described in detail above, will be additionally described below. 1. Compound C is added in an amount of 10 to 100 parts by weight of Compound A.
A method for producing a polyamic acid which is present in an amount of 1000 parts by weight. 2. Compound A is butanetetracarboxylic dianhydride,
1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, tetracyclo [6,2,1,1,0 ^2,7 ] dodeca-4,
5,9,10-tetracarboxylic dianhydride, 1,3,3a,
4,5,9b-hexahydro-5- (tetrahydro-2,
5-dioxo-3-furanyl) -naphtho [1,2-c]
-Furan-1,3-dione, pyromellitic dianhydride,
3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride, 3,3', 4,4'-biphenylsulfone tetracarboxylic dianhydride, 3,3 ', 4,4'-perfluoro Isopropylidene diphthalic acid dianhydride and 3,3 ', 4,4'
-A method for producing a polyamic acid, which is at least one selected from the group consisting of biphenyltetracarboxylic dianhydride. 3. Compound B is p-phenylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl ether, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 9,9-bis (4-aminophenyl) fluorene, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,
At least one selected from the group consisting of 2-bis (4-aminophenyl) hexafluoropropane, 4,4 ′-(p-phenylenediisopropylidene) bisaniline and 4,4 ′-(m-phenylenediisopropylidene) bisaniline. A method for producing one type of polyamic acid. 4. Compound C is acetic acid, propionic acid, trifluoroacetic acid, benzoic acid, n-butyric acid, isobutyric acid, n-caproic acid,
A method for producing a polyamic acid which is at least one selected from the group consisting of isocaproic acid and formic acid. 5. A method for producing a polyamic acid, which comprises reacting compound A with compound B in the presence of a solvent. 6. A method for producing a polyimide, wherein the dehydration ring-closing reaction is carried out in the presence of a tertiary amine and an acid anhydride.

 ─────────────────────────────────────────────────── ─── Continued Front Page (72) Inventor Tadahiko Udagawa 2-11-24 Tsukiji, Chuo-ku, Tokyo Within Nippon Synthetic Rubber Co., Ltd. (72) Inventor Yasushi Matsuki 2-11-24 Tsukiji, Chuo-ku, Tokyo Within Nippon Synthetic Rubber Co., Ltd.

Claims (2)

[Claims] 1. A method for producing a polyamic acid, which comprises reacting a tetracarboxylic dianhydride and a diamine in the presence of a compound containing one carboxyl group in the molecule. 2. A method for producing a ring-closed polymer of polyamic acid, which comprises subjecting the polyamic acid produced by the method according to claim 1 to dehydration ring closure.