DE1770365B2 - HIGH MOLECULAR, AROMATIC POLY- (ETHER-AMIDE-OXADIAZOLE) AND PROCESS FOR THEIR PRODUCTION - Google Patents

Description

- o

Hal-C-Ar ₁ -C-Hal

Il "Il ο ο

in which a halogen atom and an divalent aromatic radicals, which are optionally substituted by halogen atoms or lower alkyl radicals, and in which Ao can also consist of two aromatic radicals separated by ether or sulfonic groups, with aromatic aminocarboxylic acid hydrazides in polar organic solvents at temperatures between characterized -10 and +30 ⁰ C, the thus obtained are poly (ether-amide-hydrazide) annealed after removal of the solvent and drying at temperatures between 200 and 35O ⁰ C in that, as aromatic Aminocarbonsäurehydrazide Aminoaryloxycarbonsäurehydrazide of the general formula

H ₂ N-Ar ₁ -O-Ar ₂ -C-NH-NH,
O

in the An and Ar2 the same or different mean divalent aromatic radicals, optionally with halogen atoms or lower alkyl radicals are substituted, uses.

2. The method according to claim 1, characterized in that the annealing in the presence of Air carries out.

3.High molecular weight aromatic poly (ether-amide-oxadiazoles) insoluble in organic solvents, consisting of repeating structural elements of the general formula

Cl

and Ar, the leftovers

mean, and the phenyl radicals marked with a * correspond to An, wherein the softening point of the poly (ether-amide-oxadiazo Ie) is above 300 ⁰ C.

N N

Il Il

-C-NH-Ar ₁ -O-Ar ₂ -C C-Ar ₁ -

0 Ό '

wherein —Ar, —O — Ar ₂ - are the radicals

Cl

The invention relates to high molecular weight, aromatic poly (ether-amide-oxadiazoles) and a method for their manufacture.

It's from Journal of Pol. Sei., Part B, Polymer Letters, Vol. 5 (1967), pp. 807 to 812, high-melting aromatic poly (amide hydrazides) by condensation of aromatic dicarboxylic acid halides such. B. Iso- or terephthaloyl chloride, with aromatic Aminocarboxylic acid hydrazides, such as. B. p-aminobenzhydrazide, to divide. The disadvantage of these polymers is their relatively poor solubility in polar organic

(10 see solvents. This is how poly (amide hydrazides) from p-aminobenzhydrazide and iso- or terephthaloyl chloride in their production in dimethylacetamide off after a short time. Also in N-methylpyrrolidone are poly (amide hydrazides) from p-amino-benzhy-

ii5 drazid and terephthaloyl chloride at room temperature poorly soluble and precipitate when the solution has stood. This difficult solubility makes processing these polycondensation products made more difficult.

It is also known to produce poly (amidoxadiazoles) from these poly (amide hydrazides) by thermal treatment to produce, the ring closure to the oxadiazole group at the hydrazide group

However, it is a disadvantage of the known poly (amidhydrazides) that their conversion to the poly (amidoxadiazoles) must be carried out in vacuo or in the presence of nitrogen.

It has now been found that one arrives at significantly better ι ο soluble poly (amide hydrazides) if one as described in detail in the claimed process, the aromatic dicaibonic acid halides with the aromatic aminoca'-bonsäurehydraziden containing ether groups converts, and that this polyether 15 amide-hydrazide) surprisingly convert to poly (ether-amide-oxadiazoles) even in the presence of air permit. . . ,,, · U

So there were new high molecular weight, in organic solvents insoluble aromatic poly (ether; c amid-oxadiazole), consisting of repeating Structural elements of the general formula de. Terephthalic acid and isophthalic acid dichloride are preferred used.

As aromatic aminoaryloxycarboxylic acid hydrazides which are used for the process according to the invention can be used and represented by the general formula

H ₂ N-Ar ₁ -O-Ar ₂ -C -NH-NH, O

N-Lc-NH-Ar ₁ -O-Ar ₂ -C Il ο

-N C-Ar ₃ -I-

2S

wherein Ar ₁ , Ar 2 and Ar _{3 have} the meaning given in claim 3, the softening point of the poly (ether-amide-oxadiazoles) being above 300 ° C. A process for the preparation of these high molecular weight aromatic poly (ether-amide-oxadiazoles) has also been found, which is characterized in that aromatic dicarboxylic acid dihalides of the following general formula with aromatic aminoaryloxycarboxylic acid hydrazides of the following general formula in polar organic solvents at temperatures between -10 ° C and + 30 ⁰ C converts and the resulting poly (ether-amide hydrazide) after removal of the solvent and drying at temperatures between 200 and 350 ⁰ C

⁶¹ RIr the polycondensation dicarboxylic acid dihalides of the general formula

Hal-C-Ar ₃ -C-Hal

3 °

Il ο

Il ο

used, wherein Ar ₃ bivalent aromatic radicals which are optionally substituted by halogen atoms or lower alkyl radicals, and where Ar _{3 can} also consist of two aromatic radicals separated by ether or sulfonic groups and Hal is halogen. Examples are: Diphenyldicarboxylic acid dichloride 4,4 ', Diphenylätheirdicarbonsäuredichlo-

rid-4,4 ', diphenylsulfondicarboxylic acid dichloride-4,4', isophthalic acid dichloride, Terephthalic acid dichloride and the corresponding dibromides as well as alkyl and halogen substitution products of the listed acid halogen

C -NH- ^ f

in which An and Ar _{2 are} divalent aromatic radicals which are optionally substituted by halogen atoms or lower alkyl radicals, the following compounds may be mentioned by way of example:

4- (4'-aminophenoxy-benzhydrazide

3- (4'-aminophenoxy) benzhydrazide

4- (4'-Amino-2'-chlorophenoxy) benzhydrazide

3- (4'-Amino-2'-chlorophenoxy) benzhydrazide

4- (4'-aminophenoxy) -3-chlorobenzhydrazide

4- (4'-Amino-2'-chlorophenoxy) -3-chlorobenzhydrazide
3- (4'-aminophenoxy) -4-chlorobenzhydrazide

The polycondensation to the poly (ether-amide-hydrazides) takes place in polar organic solvents, such as Ν, Ν-dialkyl carboxamides, for example Dimethylacetamide or N-substituted lactams, such as. B. N-methylpyrrolidone.

The great advantage of these solvents is that you can work in the absence of additional acid acceptors. Highly viscous polycondensate solutions are formed when the acid halide and the aromatic aminocarboxylic acid hydrazides containing ether groups mentioned above are used in equivalent or almost equivalent amounts. The condensation is carried out at temperatures between -10 and + 30 ⁰ C. The solids content of the solution is 5 to; 40%, preferably 10 to 25%.

The highly viscous polymer solutions obtained can be added at temperatures between 50 and 225 ° C Process films and threads, but can also be processed by spinning in a felling bath.

Thermal treatment of the films and threads at temperatures between 200 and 350 ^° C. converts the hydrazide groups into oxadiazole groups, even in the presence of air. These annealed films and threads are insoluble in organic solvents and have a softening point above ⁰ C is 3CO.

From 4- (4 '■ aminophenoxy) benzhydrazide

.is

40

4s

H, N-

and terephthaloyl chloride are used according to the specified Process in the first stage poly- (ether-amide-hydrazide) obtained by the following formula reproduced repeating structural elements have:

V-C-NH-NH C

"II Il

O C

U.

The poly (ether-amide-oxadiazole) obtained from this polycondensate by tempering at 250-300 ° C shows this by the following form; reproduced repeating structural element on:

- N

-C-NH

The aromatic Aminoaryloxycarbonsäurehydrazide used to produce the polymers can be prepared by known processes as follows: hydroxybenzoic acids that can possibly be further substituted by halogen or lower alkyl groups, are ah Dinairium- or dipotassium salts, eg. B. with 4-chloro- or 3,4-dichloro-nitrobenzene in dimethyl sulfoxide, converted to Nkroaryloxybenzoic acids. The carboxylic acids are converted into the corresponding: o Esters and hydrogenated to the aminoaryloxybenzoic acid esters, which are then reacted with hydrazine hydrate to form the aminoaryloxybenzhydrazides.

In the following examples, parts by weight are related to parts by volume as kg is to liter.

example 1
a) methyl 4- (4'-aminophenoxy) benzoate

273 parts by weight of 4- (4'Nitrophenoxy) -benzoic acid methyl ester (mp .: 106-108 ⁰ C) are catalytically in 1000 parts by volume of dioxane or dimethylformamide at 50 ⁰ C and a hydrogen pressure of 60 Atü in the presence of 60 Gewichisteilen Raney nickel "B" hydrogenated. The Raney nickel is filtered off with suction while it is hot and evaporated to almost dryness in vacuo. The product becomes crystalline upon addition of water. It is filtered off with suction and recrystallized from alcohol. There are 210 parts by weight = 86.5% of theory. Theory 4- (4'-Amino-phenoxy) -benzoic acid methyl ester of melting point 90-9TC obtained.

b) 4- (4'-aminophenoxy) benzhydrazide

243 parts by weight of 4- (4'-aminophenoxy) -benzoic acid methyl ester are heated to 200 ° C for 4 hours with 300 parts by volume of hydrazine hydrate.

Then it is diluted with about 1000 parts by volume of water, suctioned off and made of alcohol or Dioxane recrystallized.

Yield: 218 parts by weight = 89.5% of theory. Fp .: 169-170 ⁰ C.

c) Representation of the poly (ether-amide-hydrazide)

243 parts by weight of 4- (4'-aminophenoxy) benzhydrazide are dissolved in 1350 parts by weight of dry N-methylpyrrolidone. 203 parts by weight of terephthaloyl chloride are then added in portions at 5-15 ° C. A highly viscous solution is obtained which is diluted with a further 500 parts by weight of N-methylpyrrolidone. The poly (ether amide hydrazide), which can be isolated from the solutions by precipitating with water, has a relative solution viscosity, measured at 20 ¹ C on a 0.5% solution of the polycondensate in N-methylpyrrolidone, of 3.25.

d) Representation of the poly (ether-amide-oxadiazole)

The polymer solution obtained according to Ic is streaked on Glasolatten into thin films, which are dried in an oven at 120-140 ⁰ C for 2-3 hours. The clear films are then detached from the glass plates and suspended in a drying cabinet in which they are first heated for one hour at 18O ⁰ C and then for 2 to 3 hours at 250-27O ⁰ C. After this time, as the IR spectrum shows, the hydrazide structures of the polycondensate have almost completely converted into oxadiazole units. The polymers are now no longer soluble even in boiling N-methylpyrrolidone. At 305 ^° C., the films have not yet become brittle after 4 weeks.

The softening point of poly (ether-amide-oxadiazole) is above 350 ° C.

Example 2

If Ν, Ν-dimethylacetamide is used in Example Ic instead of N-methylpyrrolidone, but otherwise as described there, one also obtains highly viscous poly (ether-amide-hydrazide) solutions which, as described in Example Id, form films can be processed. The conversion to poly (ether-amide-oxadiazoles) is carried out as in Example Id. The softening point of the poly obtained (ether-amidoxadiazols) is above 350 ⁰ C.

Example 3

If the same amount of isophthaloyl chloride is used in Example Ic instead of the terephthaloyl chloride used there, but otherwise under the same conditions as described there, one obtains highly viscous poly (ether-amide-hydrazide) solutions which are processed further as in Example Id can. The thus obtained poly (ether-amide-oxadiazole) embrittlement at 300 ⁰ C for several weeks and is insoluble in boiling N-methylpyrrolidone. The softening point of the poly (ether-amide-oxadiazole) is above 350 ⁰ C.

Example 4

243 parts by weight of 3- (4'-aminophenoxy) benzhydrazide are used in 1350 parts by weight of N-methylpyrrolidone reacted analogously to Example Ic with 203 parts by weight of terephthaloyl chloride. The relative solution viscosity of the poly (ether amide hydrazide), measured as in Example Ic, is 2.25.

Analogously to Example Id, the hydrazide structures of the polycondensate can be converted into oxadiazole units will. The softening point of this poly (ether amide oxadiazole) is above 350 "C.

The 3- (4'-aminophenoxy) -benzhydrazid, mp .: 116-118 ⁰ C may analogously to Example la and Ib from 3- (4'-aminophenoxy) -benzoic acid ethyl ester are obtained.

Example 5

If the terephthaloyl chloride used there is replaced by isophthaloyl chloride in Example 4, but otherwise as described there, a poly (ether-amide-hydrazide) is obtained, the relative viscosity of which is measured as in Example Ic. Is 1.85. The conversion to the poly (ether-amide-oxadiazole) is performed by heating for 24 hours of 220 - is 240 "C. Its softening point above 350 ⁰ C.

Example 6

277.5 parts by weight of 3- (4'-amino-2'-chlorophenoxy) benzhydrazide (melting point 162-65 ° C.) are reacted analogously to Example Ic) in 1450 parts by weight of NMethylpyrrolidone or dimethylacetamide with 203 parts by weight of terephthaloyl chloride. The relative solution viscosity of the poly (ether-amide-hydrazide) obtained, measured as in Example Ic), is 2.15. The hydrazide structures of the polycondensate are converted into ι ο oxadiazole units analogously to Example Id). The softening point of the poly (ether-amide-oxadiazole) is above 350 ⁰ C.

The 3- (4'-Amino-2'-chlorophenoxy) -benzhydrazid was prepared from 3- (4'-Amino-2'-chlorophenoxy) benzoic is säuremethylester (mp. 91-94 ⁰ C) obtained by hydrogenating the corresponding Nitroesters (mp. 73-76 ⁰ C) is accessible.

Example 7 and 8

If, in Example 6, instead of the 3- (4'-amino-2'-chlorophenoxy) benzhydrazide used there, the same amount of 4- (4'-amino-2'-chlorophenoxy) benzhydrazide (melting point 181-84 ° C.) is used ) or 4- (4'-aminophenoxy) -3-chlorobenzhydrazide (melting point 199-203 ⁰ C), but otherwise as described there, poly (ether-amide hydrazides) are obtained which have a relative solution viscosity of 2, 45 and 2.60 respectively. The ring closure to the poly (ether amide-oxadiazoles), whose softening points are above 350 ° C., takes place as indicated in Example 1 d).

The 4- (4'-amino-2'-chlorophenoxy) - and the 4- (4'-aminophenoxy) -3-chlorobenzhydrazide were from the corresponding monochloraminophenoxybenzoic acid methyl esters (Mp. 85-88 or 97-100 ° C) shown by catalytic hydrogenation of the corresponding Nitroester (m.p. 135-39 or 126-27 ° C) obtained became.

Example 9

312 parts by weight of 4- (4'-Amino-2'-chlorophenoxy) -3-chlorobenzhydrazide (Fp. 188-92 ⁰ C) analogously to Example la) and Ib) from the corresponding dichloro-nitrophenoxybenzoesäuremethylester (Fp. 118-20 ⁰ C) by catalytic hydrogenation to Dichloraminophenoxybenzoesäuremethylester (mp. 89-93 ⁰ C) is represented, as implemented in example Ic) in 1550 parts by weight of dry dimethylacetamide with 203 parts by weight terephthaloyl chloride. The value obtained for the relative solution viscosity is 2.40.

The conversion to the poly (ether-amide-oxadiazole) having a softening point above 350 ⁰ C, is carried out as in example Id).

Example 10-13

If the same amount of isophthaloyl chloride is used in Examples 6-9 instead of the terephthaloyl chloride used there, but if the procedure is otherwise as indicated in these examples, then highly viscous poly (ether-amide-hydrazide) solutions are obtained as indicated in Example 5 to poly (ether-amide-oxadiazoles) with a softening point above 300 ⁰ C are converted.

Claims (1)

'L patent claims: 1. Process for the production of high molecular weight aromatic poly (ether-amide-oxadiazoles) by reacting dicarboxylic acid halides of the general formula Cl