DE1770365C3 - High molecular weight, aromatic poly (ether-amide-oxadiazoles) and processes for their production - Google Patents

Description

ll.i

Ar ₁

C ll.il

(I.

in which a halogen atom and kind of divalent aromatic radicals, which are optionally substituted by halogen atoms or lower alkylresie, and in which Ar, can also consist of two aromatic radicals separated by ether or sulfonic groups, with aromatic aminocarboxylic acid hydrazides in polar organic solvents at temperatures / wipe -IO and t-JO ¹ C ". The poly- (Äihei-amid-hydra / iiles) thus obtained are tempered after removal of the solvent and drying at temperatures between 2 (M) and 150 ° C, characterized in that as aromatic Aminocarbonsäurehydra / ide Aminoaryloxyearbonsäurehydra / ide of the general formula

Cl Cl
C!

and Λi "j the red one

ILN Ar, O Ar, C Ml NII,
O

in the An and Ar. · same or different mean divalent aromatic radicals, which are optionally replaced by haloamines or lower alkylre they are substituted.

2. The method according to claim I. characterized by that the tempering was carried out in the presence of air:

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

SO,

mean, and the phenyl radicals marked with a * correspond to An, wherein the softening point of the poly (ether-amide-oxadiazo Ie) above is of J00 ^u C.

N N

C NII Ar, O Ar, CC Ar ₁

O O

where Ar, O Ar, the residues

(ι

(I.

The invention relates to high molecular weight aromatic poly (ether-amidoxadiazoles) and a Ver falces for their production.

It 's from Journal of Pol. Sci., Part B, Polymer Letters Vol. ·} (1967), pp. 807 to 812 known, 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-aminobenz hydrazide to produce. The disadvantage of these polymers is their relatively poor solubility in polar organic solvents. For example, poly (amide hydrazides) from ρ aminobenzhydrazide and iso- or terephthalic chloride precipitate after a short time when they are produced in dimethylacetam. Benzhy dra / id and lerephthaloyl chloride are sparingly soluble at room temperature and fall out when the solution is standing. This poor solubility makes the processing of these polycondensation products difficult.

It is also known that these poly (umid-hydraziden) to produce poly (amidoxadiazoles) by thermal treatment, with the hydrazide group the ring closure to the oxadiazole group takes place.

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

It has now been found that significantly more soluble poly (amide hydrazides) can be obtained if as described in detail in the claimed process, the aromatic dicarboxylic acid halides with the aromatic aminocarboxylic acid hydrazides containing ether groups converts, and that this poly (ether amide hydrazide) surprisingly also in the presence let the air convert to poly (ether-amide-oxadiazoien).

So there were new high molecular weight, in organic solvents insoluble aromatic poly- (ether-amide-oxadiazoie) found, consisting of repeating structural elements of the general formula

[I.

-C NU Ar ₁ O -Ar, C

Ar, -

in which An, Ar? and \ n are as defined in claim 3 have the Erwe-chungspunki the poly (ether-amide-oxadiazole) above is 300 ⁰ 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 ⁰ C and + 30 ° C and the resulting poly (ether-amide hydrazide) is annealed at temperatures between 200 and 350 ⁰ C after removal of the solvent and drying.

Dicarboxylic acid dihalides of the general formula are used for the polycondensation

Hai -C '-' - Ar, --C - Hiil

f)

used, wherein An divalent aromatic radicals, the are optionally substituted by halogen atoms or lower alkyl radicals, and where An also consists of two aromatic radicals separated by ether or sulfonic groups and Hai halogen means. Examples are: Diphenyldicarboxylic acid dichloride-4,4 ', Diphenylätherdicarbonsäuredichlo-

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 halides. Terephthalic acid and isophthalic acid dichloride are preferred used.

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

H, N Ar, O Ar, C NU NIJ, O

are shown in which An and Ao bivalents aromatic radicals which are optionally substituted by halogen atoms or lower alkyl radicals may be The following compounds are mentioned as examples:

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 (ätlicramid-hydraziden) takes place in polar organic solvents, such as Ν, Ν-dialkyl carboxamides, for example Dimethylaeetarnid or N-substituted lactams,

ν, such as B. N-methylpyrrolidone.

The great advantage of these solvents is that they can be used in the absence of additional acid acceptors can work. It is formed when the acid halide and the above-mentioned aromatic

vs see, aminocarboxylic acid hydrazides containing ether groups used in equivalent or almost equivalent amounts, highly viscous polycondensate solutions. The condensation is carried out at temperatures between -10 and + 30 ° 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.

₄ s By thermal treatment of the films and threads at temperatures between 200 and 350 ^° C., the hydrazide groups are converted into oxadiazole groups, even in the presence of air. These annealed films and threads are insoluble in organic ones

so solvents and have a softening point which is above 300 ⁰ C.
Auu4- (4'-aminophenoxy) benzhydric acid

H ₂ N-

-O

C-- NfI-NH ₂ C)

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:

-C NH

Il ο

C ^- -NU NH C

The polycondensate from this by annealing at 250-300 C resulting ^poly-n (ether-amide oxadiazol), the by the following [ormcl reproduced repeating Sirukturclemeni to:

C NU

The aromatic aminoaryloxycarboxylic acid hydrazides used to prepare the polymers can be prepared by known processes as follows: Hydroxybenzoic acids, which may also be substituted by halogen or lower alkyl groups, are used as disodium or dipotassium salts. z. B. with 4-chloro- or 3,4-dichloro-nitrobenzene in dimethyl sulfoxide. converted to nitroaryloxybenzoesäurcn. The carboxylic acids are converted into the corresponding ν F.sier and hydrogenated to the aminoaryloxybenzene acid esters, which are then reacted with hydrazine hydroxide to form the aminoaryloxybenzhydrazides.

Weight parts behave in the following examples to volume parts as kg to 1 liter. :

Example I.
a) Methyl 4- (4'-aminophenoxy) benzocate

273 parts by weight of 4- (4'-Niirophenoxy) -benzoesäurcmethylester (m.p .: 106-108 ⁰ C) in 1000 parts by volume of dioxane or dimethylformamide at 50 ° C and a hydrogen pressure of 60 Atü in the presence of 60 parts by weight of Raney nickel "B" catalytically 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) -ber, 'oesäuremethylester obtained with a melting point of 90-91'C.

b) 4- (4'-aminophynoxy) -benzhyörazide

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 about 1000 Volumtciien of water is diluted, sucked off and made of alcohol or Dioxane recrystallized.

Yield: 218 parts by weight = 89.5% of theory. Fp .:! 69-170 "C.

c) Representation of the poly- (älhcramid hydra / .ids)

243 parts by weight of 4- (4'-aminophynoxy) -ben / hydrazide are dissolved in 1350 parts by weight of dry N-methylpyrrolidone. At 5- ITC, 203 parts by weight of terphlhaloyl chloride are then added in portions. 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 precipitation with water has a relative solution viscosity. measured at 20 (on a 0.5 "/ o solution of the polycondensal in NHylpyrrolidone. of i.2 ^r >.

d) Representation of the poly (athcr aiiud-oxiidiii / .ols)

The Polymcrlosting obtained after U is on Glass plates / ii streaked out in films, which in a drying cabinet at 120 - 140 C for 2 — J Hours to be dried. The clear films are then detached from the glass plates and placed in a Hanged in a drying cabinet in which it was first set to 180 C for one hour and then left on for 2 to J hours 250 - 270 C heated. After this time, as the IR spectrum shows, the hydraid structures have emerged of the polycondensate almost completely in oxadia / oleinhei th converted. The polymers are now no longer soluble even in boiling N-methylpyrrolidone. the Films are not yet brittle at 305'C after 4 weeks.

The softening point of poly- (aihcr-amid-oxadiazole) is above 350 C.

Example 2

If NN-dimethyl acetamide is used instead of N'-methylpyrrolidone in Example Ic, but if the sunsi is used as described there, then one obtains, if necessary, highly viscous Polv-iäiher-arnid-h ^v dr37id} -solutions-'CP. which can be processed into films as described in Example Id. The conversion to poly (ether-amide oxadiazoles) is carried out as in Example Id. The softening point of the poly (ether-amidoxaciiazole) obtained is above 350 C.

Example 3

κ; In example Ic instead of using there ten terephthaloyl chloride, the same amount of isophthaloyl chloride. but otherwise work under the same Conditions as described there result in highly viscous poly (ether-amide-hydrazide) solutions. the

n can be further processed analogous to example Id. The thus obtained poly (ether-amide-oxadiazole) embrittlement at 300 "C for several weeks and insoluble in boiling n-Melhylpyrrolidon. The softening point of the poly (ether-amide oxadiazois) Liegi oberhalb350 ⁰ C.

Example 4

243 weight 3- (4'-aminophenoxy) -ben / .hydra- ^ s zid are in 1350 Gewichuicilen N Mcthylpyrrolidon analogous to example 1c with 203 weight of the Terephlha implemented loyl chloride. The relative solution viscosity of the poly (ether-amide-hydrazide), measured as in Example Ic, is 2.25.

μ. Analogous to Example Id, the hydra / id structures of the Pdlykondcniats converted into Oxadiazolcinhciien will. The softening point of this poly (ä:! Ier amide-oxadiazoles) is above 350 "C.

The 3- (4'-Aininophenoxy) -benzhydrazid mp.> Λ 116- 118 ^J C can analogously to Example la and 'b from 3- (4'-Aminophetioxy) -benzocsäureälhylcs "cr are erhallen.

Example 5

F.rsct / .t is used in example 4 there Isophthalyl chloride by isophthalyl chloride. is working but otherwise as described there, you get tin Poly- (ether amid-hydra / .id). its relative viscosity. (■ ·. Measured as in example Ic. 1.85 contributes to the Conversion / u the P:) ly- (äthcr-amid-oxiidia / ol) er follows by heating for 24 hours from 220-24 (1 ( Its softening point is above 350 (

I) c i s ρ ι e I (ι

27 7. ^r ) (iwichtstcile J (4 'Amino 2' -chlorophynoxy) ben / hydra / id (Ip 162-65 "C) are converted analogously to Example 1c) in 1450 parts by weight of N methylpyrrolidone or dimethylacetamide with 203 (iewichisleilcn Terephihalloylchlond / The relative viscosity of the solution in solution of the erli.iltcncn poly (with amide hydraids), measured as in Example It), is 2.15 converted. The softness pn iik ι of poly (ether amide oxadia / ols) lies above 350 (

The 3 (4 'Λ mi η ο-2' ch lor phenoxy) be η / hydra / id

became from the i (4 'Amino ^' - chlorpheiioxy) ben / oe ^ acidic metliylestcr (ip. 91-94 ° C) represented by I lydriei en of the opposing Nilroester (Pp 7 j- 7h C) / is unavailable.

He ι s pi el 7 and H

In example 6, instead of the 3- (4'-amini>-2'-chl (irphenoxy) -bcn / hydra / ids used there, the same amount of 4- (4'-amino-2'-chlorophynoxy) -hcn / hydra / id (Ip IHI-84 "C) or 4- (4'-aminophenoxy) -Jchlorben / hydia / id (Cp. 199-203 ° C), but otherwise works as described there , we obtain poly (ether-amide hydrazide) having a relative l.ösungsviskosität of 2.4 ¹ J b / w have 2.60 the ring closure to the poly (älhcramid'OXiidiazolen) whose ^Q:.. .rweichungspunkte above J50 "C are carried out as specified in Example Id). \ <

The 4- (4'-Amino-2 ^r chlorophenoxy) - and 4 (4'-aminophenoxy) 3-chloro-ben / hydrazide were prepared from the corresponding Monochloraininophenoxybcnzoesau remethylestcrn (l ^/ .w p 85-88 B 97.. - I (K) "C), which were obtained by catalylic hydrogenation of the corresponding nitroester (f ρ US-39 or 126-27" ()

Example 9

312 (iwichtstcile 4 (4 'Amir.o 2'chlorphenoxy) 3 L'hlcirbcn / hydra / .id (I ρ 188-12 "(I), the analogous example la) and Ib) from the corresponding dichloronitrophynoxyben / ocsäiiremethylester (Ip. 118-20 "C") according to catalytic hydrogenation to dichloroaminophenoxyben / ocsäuremethylester (Ip. 89-93 "C) can be represented, is as in Example Ic) in 1550 parts by weight dry dimethylacelamide with 203 parts by weight lerephthaloyl chloride repositioned. The received Wen Eggs relative i.ösuugsviskosiiäi iiegi at 2.40.

The conversion to poly (ether amide oxadia / ol) whose (-! Rwcichungspunkl is above 35O "C) takes place as in example Id)

Example 10-13

If one uses in ilen Examples 6 - 9 instead of the The phthaloyl chloride used there contains the same amount of isophthalyl chloride, but otherwise works as in Given these examples, one also obtains highly viscous poly (ether-amide hydrazide) Ixisungen which as stated in example 5 for poly (ether-amide-oxadia / olcn) with a boiling point above 300 "C be reversed.

Claims (1)

Patent claims: 1. Process for the production of high molecular weight aromatic poly (ether-amidoxadiazoles) by reacting dicarboxylic acid halides of the general formula Cl