JPS60181127A - Polyazomethine resin and its production - Google Patents

Abstract

PURPOSE:To provide the titled resin soluble in organic solvents, moldable easily, having excellent heat-resistance and electrical properties, and useful as industrial materials, by reacting a specific diamine with a specific dialdehyde in an organic solvent. CONSTITUTION:The objective resin of formula III can be produced by reacting (A) the diamine of formula I (Ar is bivalent tetraphenylthiophene group which may contain bivalent aromatic group as a part thereof) [e.g. 2,5-bis(4-aminophenyl)-3,4-diphenylthiophene] with (B) the dialdehyde of formula II (R is bivalent organic group), (e.g. isophthalaldehyde) in an organic solvent such as o- chlorophenol, usually at 0-200 deg.C for several tens minutes - several days.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a novel polyazomethine resin and a method for producing the same.

Prior Art Polyazomethine resin has been known as a material with excellent heat resistance. However, since many of these polyazomethine resins are insoluble in various organic solvents and thermally infusible, it has been extremely difficult to mold them.

DISCLOSURE OF THE INVENTION The present inventors have made earnest efforts to overcome the above-mentioned drawbacks and to produce polyazomethine resins that are soluble in various organic solvents, and have completed the present invention.

The first invention of the present invention is based on the general formula % (%) () (wherein R is 1 yuzu or two or more divalent atoms 1LAr is A
When r is 1 yuzu, divalent tetraphenylthiophene 1,
When there are two or more types of Ir, one of them is a divalent tetraphenylthiophene group, and the other type is a divalent aromatic M
, n is an integer from 10 to 200).

The second invention of the present invention is based on the general formula % formula % () (wherein R is one or more divalent organic groups, and Ar is a divalent tetraphenylthiophene group when there is one type of Ar. , when Ar is two or more types, one of them is a divalent tetraphenylthiophene group, the other type is a divalent aromatic M, n is an integer of 10 to 200). In producing the general formula % formula % () (in the formula, Ar is a divalent tetraphenylthiophene a when there is one type of Ar, and a divalent tetraphenylthiophene a when there are two or more types of h'', as one of them). using the tetraphenylthiophene method of This is a method for producing a polyazomethine resin, in which one or more dialdehydes represented by (representing a divalent organic group) are reacted in an organic solvent.

The polyazomethine resin represented by the general formula (I) of the present invention has the characteristic that it can be obtained as an organic solvent solution by the above-mentioned production method of the present invention, and molded products such as polyazomethine resin films can be easily molded from this solution. Its industrial value is extremely high.

The polyazomethine resin represented by the above general formula (I) is composed of a diamine represented by the above general formula (n) and the above general formula (M
), but as the diamine, the diamine of the above formula (U) in which Ir is a divalent tetraphenylthiophene group can be used alone, or 20 to 99 mol% The above Ar is a diamine consisting of a tetraphenylthiophene group,
A diamine in which 1 mol % of the above Ar is composed of one or more divalent aromatic groups can also be used in combination with other species. When using a mixture of diamines, the diamine consisting of divalent tetraphenylthiophene groups is 20 mol%.
If it is less than this, the solubility of the produced resin in organic solvents, which is a feature of the present invention, will not be sufficiently satisfied. As the thiamine represented by the above general formula (...), a diamine in which Ar is a divalent tetraphenylthiophene group is used alone, and two or more types of dialdehydes represented by the above general formula (II) are mixed. You can also use

Among the diamines represented by the above general formula (II), lr
The diamine consisting of a divalent tetraphenylthiophene group refers to 2,5-bis(4-aminophenyl)-3,4-diphenylthiophene. It is known that this diamine can be produced from cyclized benzyl and sulfur, which are industrially available at low cost. For example, Be Dilty et al. (W
, Dilthey) in J. Prakt, Ohem, Vol. 2, pp. 151 and 257 (4988).

Among the diamines represented by the above general formula (n), examples of diamines consisting of a divalent aromatic group include metaphenylenediamine, paraphenylenediamine, 8.8'-diaminobiphenyl, 4.4'-diaminobiphenyl, 8.8'
-methylene dianiline, 4.4'-methylene dianiline, 4.4'-ethylene dianiline, 4.4'-isopropylidene dianiline, 8.3'-oxydianiline, 4
．． 4'-oxydianiline, 8.4'-oxydianiline, 8,8'-thiodianiline, 4.4'-thiodianiline, 8.8'-carbonyldianiline, 4.4'-carbonyldianiline, 8. Examples include 8'-sulfonyldianiline, 414'-sulfonyldianiline, 1,4-naphthalenediamine, 5-naphthalenediamine, and 2,6-naphthalenediamine.

Examples of the dialdehyde represented by the above general formula (ll) include terephthalaldehyde, iso7taldehyde, 1,
4-S7thalenedialdehyde, 1,6-naphthalenedialdehyde, 2,6-naphthalenedialdehyde, 4t4'
-diphenyl ether dialdehyde, 818'-diphenyl ether dialdehyde, 4.4'-diphenylmethane dialdehyde, 8.8'-diphenylmethane dialdehyde, 4+4'-diphenylsulfone dialdehyde, 8
．． Examples include 8'-diphenylsulfone dialdehyde.

1 of the polyazomethine resin represented by the above general formula (1)
1! The production method is to react the diamine compound represented by the above general formula (Il) and the dialdehyde represented by the above general formula (I[) in an organic solvent at 0 ° C to 200 ° C for several tens of minutes to several days. It is done. In this method, the molecular weight of the polyazomethine resin represented by the general formula (I) is limited by the charged amounts of the diamine compound represented by the general formula (II) and the dialdehyde represented by the general formula (III), and these reaction components By using equimolar amounts of , it is possible to produce a polyazomethine resin represented by the above general formula (I) as a polymer. The reason why n is limited to an integer of 10 to 200 in the polyazomethine resin of general formula (I) is that if n is smaller than 10, the mechanical properties and heat resistance of the molded product, such as a film, will not be sufficient. ,
This is because when n exceeds 200, solubility in organic solvents and moldability deteriorate.

Organic solvents that can be used in this method include amide solvents such as NlN-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone, amide solvents such as dimethyl sulfoxide and tetramethylene sulfone, anisole, and diphenyl ether. Examples include benzene-based solvents such as , nitrobenzene, benzonitrile, cresol, phenol, and chlorophenol.

In particular, when using a solvent that can azeotrope with water, such as cresol or 0-chlorophenol, the reaction can proceed with good efficiency by distilling off these solvents from the reaction system under reduced pressure at around 100°C. .

The solubility of the thus produced polyazomethine resin represented by the general formula (I) changes depending on the type of the diamine represented by the general formula (...) used and the dialdehyde represented by the general formula (III) used. Many derivatives quickly become soluble in mineral acids such as sulfuric acid. Some derivatives include chloroform, tetrachloroethane, N,N-dimethylpolamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, and dimethylsulfate.

It becomes soluble in liquid preparations such as phoxite and cresol as they age or in some parts. The polyazomethine resin represented by the above general formula CI) is thermally stable and shows no significant change even when heated to nearly 400°C.

Examples of the invention The present invention will be explained in more detail below with reference to Examples.

Example 1 2,5-di(4-aminophenyl) -a l 4-diphenylthiophene 418: (1 mmol) was added to 5 m
) dissolved in O-chlorophenol. To this solution was added 134 m9 (1 mmol) of isophthalaldehyde under a nitrogen stream, and the mixture was stirred at 20°C for 24 hours. The obtained solution is 2
00- methanol to obtain a precipitate of polyazomethine resin, which was dried under reduced pressure at 100°C for 4 hours. The intrinsic viscosity of the resulting resin was 0.45 (0.5 l/di, N-methyl-2-pyrrolidone at 80°C).

Infrared absorption vector (K13r) cm-1: 16
20 element analysis value OHN S Bl'8V value (%) 813.72 4.66 5.4
2 6.20 Actual value (%) 82.80 4.46 5
．． 11. 6.41 The obtained beriazomethine resin is a
6(II, N-methyl-2-pyrrolidone, was soluble in tetrachloroethane.

Example 2 In the same manner as in Example 1, a polyazomethine resin was obtained from 1 mmol of 2,6-di(4-aminophenyl)-al 4-diphenylthiophene and 1 mmol of terephthalaldehyde.

The intrinsic viscosity of the resulting resin is 1.4'8 (0.59/dt
, sulfuric acid, 30°C). The obtained polyazomethine resin was soluble in sulfuric acid but insoluble in organic welding.

Example 8 In the same manner as in Example 1, 1 mmol of 2,5-di(4-aminophenyl)-8,4-diphenylthiophene, 0.8 mmol of isophthalaldehyde, and 0.2 mmol of isophthalaldehyde were prepared.
Polyazomethine resin was obtained from millimole of terephthalaldehyde.

The intrinsic viscosity of the produced resin is 0.48 (0.5 l/dt, N
-Methyl-2-pyrrolidone, 80°C].

The obtained polyazomethine resin was prepared using sulfuric acid, N-methyl-2
-pyrrolidone, chloroform, 0-chlorophenol,
It was soluble in tetrachloroethane.

Example 4 1 mmol of 2.5-
Di(4-aminophenyl)-8,4-diphenylthiophene, 0.5 mmol of isophthalaldehyde, 0
．． A polyazomethine resin was obtained from 5 mmol of terephthalaldehyde.

The intrinsic viscosity of the produced resin is 0.741 (0.59/rll
SN-methyl-2-pyrrolidone, 80°C) and ivy.

The treated polyazomethine resin is made of sulfuric acid, N-methyl-
It was soluble in 2-pyrrolidone and tetrachloroethane.

Example: By the same operation as in Example 1, 0.8 mmol of 2.5
A polyazomethine resin was obtained from -di(4-aminophenyl)-8,4-diphenylthiophene, 0.2 mmol/1z17)4,4'-diaminodiphenyl ether, and 1 mmol of isophthalaldehyde. The viscosity is 0.49 (0.59/dl,
N-methyl-2-pyrrolidone, 30″C).

The obtained polyazomethine resin is sulfuric acid, N-methyl-2-
It was soluble in pyrrolidone, tetrachloroethane, creso-h, o-chlorophenol, and tetrahydrofuran.

Example 6 0.5 mmol of 2.5-
A polyazomethine resin was obtained from di(4-aminophenyl)-8,4-diphenylthiophene, 0.5 mmol of Φ,4'-diaminodiphenyl ether, and 1 mmol of isophthalaldehyde.

The intrinsic viscosity of the produced resin is 0.62 (0.59/at t
N-methyl-2-pyrrolidone, 30°C).

The obtained polyazomethine resin was soluble in fillc acid, N-methyl-2-pyrrolidone, tetrachloroethane-1-cresol, o-chlorophenol, and tetrahydrofuran.

Effects of the Invention The present invention provides a polyazomethine resin represented by general formula (I) and an advantageous method for producing this polyazomethine resin. Most of the conventional polyazomethine resins are insoluble in organic solvents and are extremely difficult to mold, whereas the polyazomethine resin of the present invention is soluble in organic solvents, easy to mold, and has excellent heat resistance. It has great value as an industrial material because of its physical and electrical properties.

Patent applicant: President of Tokyo Institute of Technology

Claims (1)

[Claims] L general formula % formula % (wherein R is I Gft or two or more divalent organic tJ
, Ar is a divalent tetraphenylthiophene group when there is one type of Ar, and when there are two or more types of Ar, the second is one of them! 1 [
A polyazomethine resin characterized in that 1 is a divalent tetraphenylthiophene group, 2 is a divalent aromatic group, and n is an integer from 1O to 200i7). 2 general formula % formula %) (wherein R is one or more divalent '+T group, A
r is a divalent tetraphenylthiophene group when there is one type of Ar; when there is two or more types of Ar, r is a divalent tetraphenylthiophene group;
In producing a polyazomethine resin represented by the tetraphenylthiophene group of illi, divalent aromatic groups as other species, and n representing an integer of 10 to 200, the general formula % formula % (wherein Ar is If there is one type of Ar, it is a divalent tetraphenylthiophene group, and if there are two or more types of Ar, one of them is a divalent tetraphenylthiophene group, and the other type is a divalent aromatic group) One or more diamines represented by 1 and one or more dialdehydes represented by the general formula % (wherein R represents one or more divalent organic groups) 1. A method for producing a polyazomethine resin, which comprises reacting 1+i5 with (to) a solvent.