DE1570886A1 - Heterocyclic polymers and processes for their preparation - Google Patents

Description

'PATENTANWrLTI

DR. E. WIEGAND DIPL-ING. W. NIEMANN.

DR. M. KÖHLER DIPL-ING. C. GERNHARDT 157088

MONTH. HAMBURG

TEiEFON = 5554 «8000 MONKS 15, 16 Sept. 1969

TELEGRAMMEi KAUPATENT NUSSBAUMSTRASSE 10

-ff. 11 897/64 7 / Pe / Loe , ', P 15 70 886.8

Monsanto Company St. Louis, Missouri (V.St.A.)

Heterocyclic polymers and processes for their preparation

The invention relates to new condensation polymers and to a process for their production and especially to new heterocyclic polymers.

Linear condensation polymers, such as polyamides, are in the form of fibers, films, or molded articles Widely used for textiles and other technical purposes where high tensile strength and high abrasion resistance are required.

When researching polymers with improved heat resistance, various heterocyclic Polymers such as polyocadiazoles, polybenzimidazoles and Polyimides, but these compositions are obtained only with great difficulty and are difficult to process into usable items. Polybenzimidazoles are made from tetramines

BATH ORIGINAL

New documents (Art. 7 § Τ para. 2 no. 1 sentence 3 of the Änderungage3. V. 4. 9.1963

. 30 9885/157 8

1 5708 0 6 "

that are not easy to clean. These Tetramines are easily oxidized and therefore wear probably to the dark color of polybenzimidazoles .at. A substantial amount of the polymer produced is also networked. Since polyoxadiazoles are insoluble in known solvents, the oxadiazole bond is formed, after a fiber or a film is formed from a polyhydrazide. Converting a large number of Hydrazide bonds in place in a spun Fiber to oxadiazole bonds, however, greatly affects the fine structure of the fiber, possibly as a result of incomplete Conversion of hydrazide bonds into oxadiazole bonds or side reactions. Such fibers have poor physical properties, e.g. 3. low tensile strength, Heterocyclic obtained in comparison with the polyhydrazide precursors of polyoxadiazoles according to the invention Copolymers are on the other hand easily produced and easily dissolved, so that one of them Variety of shaped articles can be obtained; the bonds that are difficult to make will become preformed before polymerization. Another advantage of these polymers over the aforementioned. , known polymers is the possibility of the

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physical properties of the polymers through suitable combinations of two or more different ones set heterocyclic bonds as desired, while the known polymers essentially on a single * Type of heterocyclic units were restricted.

One purpose of the invention is to make new ones Polymer compositions.

Another purpose is the production of new heterocyclic Polymers which contain a large number of heterocyclic groups, which are regularly ordered Sequence occur, with the individual heterocyclic nuclei in the chain sequence by aromatic or aliphatic © and aromatic bonds are broken.

Another purpose of the invention is the manufacture of cords, threads and films or other shaped articles from the soluble and easily processable heterocyclic polymers obtainable according to the invention.

Other purposes and advantages are from the following Description visible «,

In general, the stated purposes of the invention realized by creating new thermal resistance provides capable masses consisting of polymers which have two or more different heterocyclic bonds

9 0 9 8 8 5/1 5 7 8 bad original

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contain in a regularly arranged sequence with aromatic or aromatic and aliphatic bonds, wherein one or more heterocyclic bonds are pre-formed in a monomer and one or more heterocyclic bonds Bonds are formed during the course of polymerization. These heterocyclic units are united by hydrocarbon bonds consisting of polyvalent hydrocarbon radicals and aliphatic, can be cycloaliphatic or aromatic with a single, multiple or fused ring structure.

The aromatic or aliphatic-aromatic bond can, for. B. consist of the following

CH, - 0 ι .3 it

where R ¹ = -0-, -S-, -C-, -S-,

CH ₃ 0

η = 1 - 10.

-C-, or "( ^CH 2) _n - where 0

The aliphatic bond can be made from

- (CH,

- ^etc · ■; ■ · - · ■

exist, where a = 1 - 10.

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r _{"-;:. ':} - -.- ■' ■ * 1570836

The hydrocarbon bond can also consist of a the heterocyclic units fused hydrocarbon ring exist. ,

.The polyvalent heterocyclic bonds can contain at least one 0, N and S and can from consist of three or more heterocyclic ring members. The radicals containing divalent heterocycles can For example, consist of the following or the like.

* -Cf ^Λ C

■ VN- n;,>) ;;:> - n.:v> .. N -— N; ^ - 'i;> ~ ^N * *' ^N - ^N

'■ "·"■' ■ '■■ ■■ "· . ··' ■:, · .: * ■■> ~ ·; ^: . ■■. ■■■ ¹ '

ΊΛν Ί

: η · ι · - ■ - ^ vji- ■ η. r ^ υ ■ π Viii »· υ. ♦ ■., ii- ·? ··.»

^{: l} aiC-N Λ ;; GH-GH .... ¹ VvCH- CK ^ _f -CH-CH, -

HG '.-''N \ -CH N- -C C ~. ■ '■' ■ -

_i __! i. \\ < ·; -Ii \ "' ii ii.' ι ü

-C ^ JC- * * ■ —G '. C--, HC ^ CH, ■ · CH ■ -

v / ^R .'...- 90-9 »8S / 1B7

- 8AD ORJGlNAL "

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where R = H or lower alkyl.

Examples of with heterocyclic units
fused hydrocarbon rings are benzimiaazole from imidazole, benzothiazole from thiazole, etc. divalent haterocycles. containing remainder with fused hydrocarbon wrestle off are z. B.

C—

I R

. , λ

, CH

Il · .- ■ C- R,

• V ■ ■■■. ^v o '■ - •., 'O ■. ο .. .'Ii. . ■ · Ii . · ■ Ii ν
V ^ r ~ ^c ^ · JZ ^ N- T I ■. Il · . I! • - Il ' O -. · Ο ο

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O . ο Ii ■ · ■ Nj 'N- * N. - <* "■: II . Il:. '· ο. O

. od * like. where R = H or lower alkyl and R ¹ = -0-.,

-S -, - S0 ₂ 7 -C-, -C- or - (CHg) _n -, where η = 1 - 10. 0

. Typical polymeric compositions encompassed by the invention are

(CH ₂ ) ₈ -

H
ι ■■■■■ ΜΙ N— -_ - ". _

(2)

<Ρ

%. H N Il ι
r-N Il - N L. N-

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BAD ORIG'NÄL

1 5 7 O 8 b 6

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ORIGlMAL BATHROOM

·: ■■ "■■: ■■■ * '1570836

- ίο -

The polymers according to the invention can be prepared by using two monomers, each contain functional groups which with the functional groups of the other to form a heterocyclic polymer react with at least two different heterocyclic bonds. The reaction can take place between an A and a B monomer, as described herein, or between two A conomers.

The A-monomer contains a heterocyclic bond and such functional groups as carboxyl, alkyl ester, phenyl ester, anhydride, amino, kydrazide, iJ-phenyl imino halide, thioamide, phenylacyl halide, xetonaldehyde, tetraazole or any other group which can be linked to the functional groups of a enter into a reaction with other A monomers or with those of a B monomer. Examples of A monomers include 2,5-bis- (p-aminophenyl} -1,3,4-oxadiazole, 2,5-bis- (m-aminophenyl) -l, 3> 4-oxadiazole, 2,5- 3is ~ (3,4-dianiinophenyl) -1,3 / 4-oxadiazole, 3j ^ -Bis- (m-aminophenyl) -4-phenyl-1,2,4-triazole, m-bis- (4-p- aminophenylthiazol-2-yl) benzene, 2,5-bis- (m-carboxyphenyl) -1,3,4-oxadiazole, 2,5-3is- (p-carboxyphenyl) -1 * 3> 4-oxadiazole, 3 , 5-bis- (m-carboxyphenyl) -4-phenyl-1 _/ 2,4-trlazole, 3,5-3is- (p-carboxyphenyl) -4-phenyl-1, 2,4-triazpl, 2.5 -Bis (m-carboxymethyl) -1,3,4-oxadiazole, 2,5 ~ bis (m-benzoylhydrazide) -1,3,4-oxadiazole or the like. The functional groups of; A- or 3 -Monomers can be formed under the specified

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"Heterocyclic bond can be implemented: a 'with a Phenacylh.al.03enid converted thioamide gives a thiasol; a ketoaldehyde reacted with a hydrazine group results in an Asia ;, a Tetrazo! Ü eiert- with a Silurian ec 5! or id eic G>: adiazole "" -; a hydrazide gives "with a phenylimino" cl: loride a ^ -Fh.enyl-1, SjA-iiriazolj, etc. These h% erocycli-SGken Bindings are in addition to those in the A-l tonors ■ already existing heterocyclic bonds formed »" An example of a reaction between A-Monerneren and vain other A-Lloncmeren is the conversion of 2,5-bis- (3,4-diaraono; jhenyl) -1,3, ^ -oxadiazole with 5, A - 3is- (m ~ carbo: cyph. enyl) -4-p; ienj'l-i , 2,4-triasol with formation of a polymer, which reliable repetitive pollen from Cxadiasol · ·, Benziraidaaol and triazole units up / down.

Llonomere B does not contain any iieterocyclic formation, but must have at least two lunictionelle groups which react with the ones of a lionomer A to form a heterocyclic bond. succinic acid, glutaric acid, Sub irinsäure, rbonsäure azelaic acid, isophthalic acid, terephthalic acid ^, bibenzoic and Naphthalindic _a. Esters of these acids, fs.B. Ethyl oxalate, ethyl adipate, diethyl isophthalate, dirnethyl isophthalate, diphenyl isox> htha lat, Dianh ^ ^r dridej z.-B. ^ yromelllthsauredianhydrid, naphthalene- '

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süuredianhydrid, bis-Cphenyldicarbonsäureanhydrid), and other acid derivatives, for example, isophthaloyl chloride, terephthaloyl chloride, N, K ^r - ^D iphenylisophthalimidoylchlorid, aromatic ^ ianiine and tetramines, for example, m-phenylenediamine, p-phenylenediamine, benzidine, ^ V-diaminodiphenyl ether, 3,3 '- Diamir.obenzidin, 3 »3 '- ^ A'-Diaciinodiphenylatlier or the like. The reaction of A monomers with B monomers is represented, for example, by the following: 2,5-bis- (m-carboxy-

. phenyl) -1,3,4-oxadiazol consists ait 3,3' ^D iarainobenzidin form, to a polymer, the recurring episodes of oxadiazole and Benzimidazoleinheiton has} 2,5-bis (m-benzoylhydrazide) - 1,3,4-oxadiazole reacts with 2T, IT ^|: -diphenylisophthalimidoyl chloride to form a polymer which contains oxadiazole and triazole units, e.g. 2,5-bis- (3,4-diaminophenyl) -1,3, 4- oxadiazole reacted with diphenyl isophthalate according to the following equation:

/ O _n

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■ ■ - 13 -. , '

This copolymer. Which is a heterocyclic Bond, the Qxadiazole, which in the tetra-amine monomer is pre-formed, and the heterocyclic benzimidazole compound, which is formed during the polymerization, illustrates the general feature of the invention. There are compositions or masses with 2, 3 or more different heterocyclic bonds established in regular succession. So can a diamine that is a preformed heterocyclic Contains bond, with a no heterocyclic bond polymerized containing monomers to form a polymer with 2 different heterocyclic bonds ber a dicarboxylic acid (or its derivative) with a heterocyclic bond can be with a tetraamine, which contains the same type of heterocyclic bond, among Formation of a polymer are polymerized, which also contains awel different heterocyclic bonds » Furthermore, a tetra-amine and a dicarboxylic acid (or their Derivative), each of which has a different type of bond, with the formation of a polymer with three different heterocyclic bonds are polymerized.

The polymerization of the polymers according to the invention can by solution polymerization procedures, interfacial polymerization procedures or by a solid state process. The application,

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BADORiGINAL

long quantities of the various reactants can in the method of the invention ACCORDANCE widely depending on the desired type and it polymer can be varied. In most cases, however, equimolar lengths of monomers can be used. The solution polymerization process is generally carried out in the following manner: A heterocyclic liquor is dissolved in a suitable solvent which is inert to the polymerization reaction. The same solvents can be used both for the heterocyclic monomer and for a two monomer, which may optionally contain one or more heterocyclic bonds. Examples of such solvents are dimethylformamide DimethyIacetamidj, i-methyl-2-pyrrolidone, ^1,5-D iniethyl-2-pyrrolidone, hexamethylphosphoramide or the like. These solvents may be given a greater efficiency in many cases by Inaia it with a small ^M narrow (up to ΛΟίο) an alkali or Brdalkalisalzes such Lithiumchlo-, chloride, Lithiumbromifl, magnesium chloride, Magnesiumbromide Be-rylliumchlorid or calcium chloride, mixed · The preferred solvents for the solution polymerization are dimethyl acetamide or imethylacetamide with a. Content of dissolved lithium chloride The solution containing the monomer

solution is preferably cooled to 20 ° to -2O ⁰ O uecL the second monomer is either as a solid or in the form of a solution in one of the above-mentioned solvents

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tel added The mixture is then stirred for a while, Ms the polymerization essentially-completed and a high viscosity is obtained. This highly viscous solution can be used directly for the production of fibers, threads or films, or the polymer can can be isolated by placing the mixture in a ; -Solvent, then washes and the polymer dries and then one in the manufacture of fibers, Thread or film to be used in making solution * For certain Kassen is a heat treatment or a chemical Treatment required to preserve the molded item (fiber, Thread, film or the like.) In a regularly arranged series of to transfer polymer containing two or more heterocycles

For polymerizations in the solid state, essentially equimolar amounts of monomers or a slight amount of the more volatile monomer can be used. Temperatures from 100 ° to 4-0O ⁰ C and pressures from 0.01 mm to pressures above eiaea? Atmospheric pressure., Can be used.

The Bolymeri ^ ate made according to the invention have many desirable properties, many of the masses or Compositions according to the invention are treatable or capable of easy handling and pliable, and can be applied directly to fibers, thread, films, or other materials. molded Objects, while other masses, those in their final or finished form of fiber, thread or film form

BATH ORIQ ¹ NAL

are untreatable, shaped as a treatable intermediate. The intermediates used in the production of these heterocyclic mis-polymers are more resistant to oxidation and various side reactions than the intermediates used in the production of other polymers known in the art. The from the M _a sgen according to the invention

received / products become usable products without any effort processed The reactions leading to the heterocyclizations can be carried out immediately or directly and easily The heat stability of certain from the masses of the Invention obtained products is superior to that of many heterocyclic polymers, which only one heterocyclic bond instead of the orderly combination of several different types of heterocyclic bonds

• contain /

fertilize according to the invention ^ JrOlymerisatmassen with different heterocyclic bonds can be made according to various procedures. So can heterocyclic Bonds are preformed or created in amine monomers or they can be in heterocyclic acid monomers (or their derivatives) are preformed or generated, e.g. in 2,5-bis- (m-carboxyphenyl) -1,3,4 · -oxadiazole or its Estersj symmetrical or asymmetrical dianhydrides, e.g. bis * (cycloocetene) tetracarboxylic dianhydride or the maleic anhydride-benzene adduct, can be used

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other functional groups that work well with react with each other to form heterocyclic bonds, can be used. By being resistant to High temperature, the low dielectric constant become the grounds of the invention for such applications useful and suitable, such as electrical insulation, technical filters, conveyor belts, tire cord, heat-resistant Parachutes (parachutes) or the like. .

The invention is illustrated below by way of examples explained in more detail in which, unless otherwise stated is, all parts and percentages are based on weight are. . ■

.V

example 1 O Γ Il Γ "ί ; '/ ■''. ^: O Il . ο t · Λ · Il • 1 - 1 '·' * ■ " J j . ■■■ ν> σ x * u> «π λ · ■ *. * * ■ ο ■

;.; - ■ · (2)> yTJdifto / aoeUo, anhydride ^ / Il ^ 'Il.

BATH

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1570856

In a conical bottle or a Kenyan flask was 2.52 g (0.01 mol) of 2,5-bis (p-aminophenyl) -1,3,4-oicadiazole in 18 ml of dry ^ imethylacefcaaaid (DiIAc). brought in, the resulting solution cooled and mixed with 2.02 g (0.011 mol) of pyranellitic dianhydride (PMDA), - ^ in process for the preparation of 2,5-bis- (p-atninophenyl) -1,5, '+ - oxadiazole and similar diamines with heterocyclic formations

is in the US patent application 3er.Ko (by Preston)

described, ^ he solution vmrde stirred for 1 hour at ^{0 0} C, then allowed to warm to room temperature. The mixture was stirred for 60 hours in order to ensure the completion of the reaction, because a nitrogen atmosphere was consumed during the course of the polymerization. After completion of the polymerization reaction, a solution of the polymer in DMAc with a solids content of ^c / o was prepared , from which films a strength of about

370 were poured and baked at 110-120 °. This group consisting of a polyamide-acid Qxadiazol Fii _me were cut into strips, iii a mixture of pyridine and acetic anhydride in the ratio 3: 1 GEFC rinsed * äelEfc each soaked for 24 hours in ^ ioxan and dried at 110 ° C. By this treatment, the polyamide-oxadiazol-acid was generated in the polyimide-oxadiazol übergeführt.Strecken at 27O ⁰ C resulted in a non-brittle film; when stretching again at 4-00-425 ⁰ C, cloudy filiae were obtained,

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the 'up in the air "to 475 ° C strips of stable at 400 °. - 4-25 ⁰ C' according to the determination by Eöntgenbeugung very crystalline and oriented IiD were · The films were strong and stretched films wurdeη for testing a thermogravimetric analysis (TGA) subjected. up to 50O ⁰ C, a weight loss of 4% of an at-ISrhitzungsgeschwindigkeit of 4.2 ° C has only been observed. The maximum weight loss per minute per minute occurred at 585 ° G on.

Example 2

CD O CO OO OO

According to the procedure described in Example 1

.were a polymerization reaction between 2.20 g of 2,5-bis

o (m-aminoplienyl) -1 _> 3, ⁱ -oxadiaaol (F. = 2 ^ 9 ° - 252 G) and 1.96 g of PMDA in 15 ml of dry DMAc carried out. The films were in an imide-oxadiazole copolymer with -regular

arranged order * of bindings transferred and proved ίθθ- against temperatures above stable/.

ι Example "3

According to the procedure of Beisoiel 1 a polymerization reaction was executed hrt, wobei73 ^"D is- 5- (m-aminophenyl) -4 ~ ph.enyl-1,2,4-triazole and 0.33 6 PMDA (pyromellitic dianhydride) ind 3» 2 ml of dry dirnetnyacetamide was used. A film was cast from the resulting solution and the film was converted into an imide-4-phenyW-driaol mixed polymer.

Example 4-

Production of 2,5-bis- (3,4 ~ diaminophenyl) -1,3,4- oxa-

diazole

COOH + SOCL

NO,

COCl

1*"' . Λ

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ßAD

■ '! - ^Τ *: Γ

-v. L?

NO ₁

NO,

NO «

• COCl + HjN>. NH ₂ * H ₂ SO ₄

CO - HN-NH- CO

NO,

NO ₇ . \

NH

NH

NH,

HCl ^

J ■■■ '-

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Δ. A 50 g portion of 3,4- ^ initrobenzoic acid was heated with 100 ml of thionyl chloride for Λ hours under ¹¹ UdCf flow. The thionyl chloride was removed and the product distilled at 182 ° 184- mm to ⁰ C at a pressure of ¹ 4, wherein 32 g of a product with a melting point of 51 ° - 52 ⁰ C were obtained.

B. The 3 »4-dinitrobenzyl chloride obtained was dissolved in 30 ml of tetrahydrofuran and, with vigorous stirring, added to a solution of 8.5 g of hydrazine sulfate, dissolved in 200 g of is and 7 / water. Then 25 g of sodium bicarbonate were added and the mixture was stirred for about 10 minutes. The product, N, N'- ^-D is- (3 _l ^ -dinitrcbenzyl) hydrazine, had a melting point of 278 ^{0 after filtration and crystallization} - 280 ⁰ C.

Analysis: calcd. C 39.99; H 1.92;: N 19.99; • found: C 39.8?;. 40.12; H 2.20; N 19.63; 19.40.

C. The dinitrohydrazide was then converted to an oxadiazole by refluxing a 25.3 portion with 250 ml of phosphorus oxychloride for 3 hours. Excess phosphorus oxychloride was then removed and the product was then washed, dried and reprecipitated. The pure 2,5-bis-C3,4-dinitrophenyl) -1,3,4-oxadiazole was recovered in a yield of 19.0 g having a melting point of 230 ° -252 ⁰ C.

Analysis: calc .: 0 41.76; H 1.50; · N 20.90.

: 0.4-1.75 ;; 4-1.98; H 2.05; 2.31; N 20.38;

20.4-3.

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D. The nitro groups were reduced to amino groups by hedging with stannous chloride (tin II chloride). One % , 02 g proportion of 2,5-bis (3, ^ - diQitrophenyl) -1,3,4-oxadiazole Viurde tait one from 50 ml of ethaQol, 50 ml of concentrated hydrochloric acid in JO g of ZiQQH chloride dihydrate horjestellt solution heated under ^ üekfluß. The mixture was cooled and a precipitate collected, washed and filtered the white

Precipitate gave 2 g of tetraamine with a melting point of

Analysis: Calculated: C 49.55 f H 5.00; N 29.99

gef '.; G 59.65 ", 59 ₅ 55i H 5.31; 5.15; N 29.82;

29.62.

E Production of oxadiazole-benzimida'zole copolymers aat by polymerization in the solid state.

In eineQ Reäktionskolben was added 1.4 g (0.01 mole) of 2,5 -! ^{-: B} is-0.4-diaminophenyl) '- 1,3,4-oxadiazol · (F' ■ 267 ° - 271 ⁰ C ) and 1.59 g (0.0.1 mol) of dipheayl isophthalate (F «13 ^ ° -135 ° G). ^T he reaction was in.einer Stickstoffatmosphä-

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-90-

o ^UQd

re at 22O ^U C for about 10 minutes / at 265 C during _a run sth 30 Minutjen. Phenol and water distilled off at the latter temperature. The polymer obtained was soluble in concentrated sulfuric acid, formic acid ethylacetamide with a content of 3% dissolved lithium chloride.

A polymer of higher molecular weight was obtained by heating 1 g of the polymer at 400 ^° C. under a pressure of 0.1 mm for 3 hours. The heat or Hitzesta / stability of this oxadiazol-benzimidazole Mis.-hpolymerisats determined by thermographic analysis, was excellent, and the following weight losses were found at various temperatures: up to 480 ⁰ C keinj to 500 ⁰ C and up to 580 ⁰ C, only 14 %.

Example 5

+ HOOC - (CH ₂ J ₈ -COOH

H. ·· ■■ '

IJ% .. (CH ₂ J ₈ - <

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The tetraamine described in Example 4 was in a proportion of 0.564 g (0.002 mol) with 0.4O4 g (0.002 mol) Sebacic acid for 2 hours and 20 minutes at 255 ° C reacted under a nitrogen atmosphere. From the polymer melt, which had a melting point of 3 ^ 2 ° C,. strings could be pulled. The polymer was too soluble in m-cresol.

Example 6

• · ιι '

'·· ■ 4 ' "1

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The procedure of Example 1 was carried out using 4.50 g (0.01 mol) of m-bis (4-p-aminophenylthiazol-2-ylbenzene), its preparation in US patent application Ser.

Nr (by Preston) in 20 ml

dry dimethylacetamide and 2.18 g (0.01 mol) PMDA (pyromellitic dianhydride). An additional 10 ml amount of dimethylacetamide was added to the solution prior to casting films. Films were a thickness of about 50Q / d (20 mils) poured at 110 ° C for 3 hours, dried and dissolved in a mixture of 3 parts of pyridine and 2 _(parts of acetic anhydride. After 16 hours the films were in dioxane for 2 hours soaked and dried. When strips of this film were stretched over a heated ceramic pin, they showed excellent thermal stability to temperatures above 425 ° C.

Example 7

Ii

OO CJI

CH ₃ CH ₂ - Q

CH CH ₂ -OC

NH ₂ -NH ₂

CO-CH ₂ CH ₃ + KOH

O '

COH

SOCi,

CH ₃ CH ₂ - O

Il

O O I! Ii CNHNH-C-

O CCl

Il

COCH ,, - CH _r

il

NH ₂ * NHC

O O

Il ü

CNH-NHC-

il

CNH -

BATH ORIGINAL

POCl ₁

NH ₂ NH ₂

NH ₀ NH-C

CCCH ₂ CH ₃

A. A 203 g portion (1.0 mole) of isophthaloyl chloride and 250 ral ethanol were stirred together until the initial exothermic reaction ceased. The solution was during

30 lanuten held at ^{£ l} ückfluß and excess ethanol was distilled off. D s _a product DiäthyIlsophthalat was g in a yield of 206 (bp ■ 175 ° - 178 ° C / 17 mm) was obtained.

. B «A solution of 55 g / of this diethyl isophthalate in 140 ml of ethanol was saponified by adding 15 g of potassium hydroxide in 15 ml of water. The gel obtained was refluxed for 30 minutes, cooled and extracted with ether to remove unreacted diester. The water was acidified and the crude acid products were precipitated. Äthylhydrogenisophthalat having a melting point of 131 ° -132 ⁰ C was prepared according to Unila? Istallisation from B-Enzol in a yield of 16.5 g.

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if

O, The ethyl hydrogen isophthalate was then replaced by thionyl chloride Converted into m-Oarbäthoxybenzoylchlorid, Kp = 6 am.

Solution of 9 g of the ^ti äurechlorids in 20 ml of tetrahydrofuran to 2.6 g Hydrazinsulf was at 100 g V / ater and, ice. Then, 8 g of sodium bicarbonate the mixture was ow suge, which was mixed for 10 minutes · The product, lT _t N ^l -6Ls- (m-carbäthoxybenzoyl) hydrazide (I) was iiltriert, washed and dried to give a yield of 7, 7 g was obtained, mp »185-187 ° 0.

Analysis: calc .: 0 62.47; H 5.25; N 7.29 ;: found s 0 62.81; H 5.42; N 7.15; 7.33.

E. The hydrogen chloride (I) was converted into an oxadiazole by reaction with refluxing phosphorus oxychloride. Excess oxychloride was stripped off and the residue was recrystallized from ethanol. Of 19, 2 g Hydraulic _a zid (I) 17.8 S 2,5-bis (m-carboäthoxyphenol) -1,3,4-oxadiazole (III) were obtained with a melting point of 133 ° C ⁰ _ 134- . Analysis: Calculated: C 65.55; H 4.96; Ή 7.65; Found: C, 65.76; 65.60; H 4.72; 5.05; N 7.54;

7.69.

P. The 2,5-bis (m-carboethoxyphenyl) -1,3,4-oxadiazole (III) was converted into a dinydrazide (IV) by a solution of 8 g of the compound (III) and 300 ml of methanol with 9 6 95 # hydrazine under reflux for J hours cooked. When the solution cooled, 2.8 g of product were with

ο a melting point of 230 to 235 0 excreted.

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soci

- / Dimethylf or mamid r. Ka ta Iysator ι

G. A portion of NjN'-diphenylisophthalamide made from isophthaloyl chloride and aniline was refluxed with a large excess of thionyl chloride using a few drops of dimethylformamide as a catalyst until solution was achieved. Excess thionyl chloride was distilled off and the residue was recrystallized from isooctane which had been dried with calcium hydride. The product, Ν, Ν ¹ -Diphenylisophthalimi- <& dyl ohlorid with a melting point of 146 ° to 150 ° C would be produced in almost quantitative yield.

NH NH-C-

• example 8th O O - Il. Il if ι » CNF C- <N- π X J

IV

BATH ORIGINAL

3o

Ii L Ij Ii if ] V-C C. N ^ - / If Il ¹ N - N -

VI

To a suspension of 1.35 S (0, C04 UoI) of the dihydrazide (^ V) from Example 7 i & 10 nil pear hylacetamide with • a content of 5 % dissolved lithium chloride vmrdenjri. Ί, ^ Ί g (0.004 mol) kjn '- ^ ipiienylisophthalimidoylchlorid (V) with a iichnielzpunkt vn * 146 ° - 150 ⁰ C added. The Llischunt; was stirred for 50 minutes for ⁰ ° C, then allowed to come to a temperature of 3 ° C and stirred for overnight. The Llischunj was then heated for 1 otunäe at 1JO ⁰ G and V / ASSOR _a usg3füllt. The melting point of the dried polymer betrüg 190 ⁰ G. .vurde Ss from a solution of the polymer ± u dime thy Iac etainid with a content of 7 "/ ό lithium chloride ID -c'ilm poured.

90 98Ö57 1578

> AL-

- Yes -

To a solution of 1.78 g (0.005 mol) of II in 12 ml of dirnetile acid amide with a content of 5% lithium chloride were added 1.77 SN, K'-dipilienylisophthalimidoyl chloride (V). The polymer solution was for 30 minutes at
G ⁰ C stirred and allowed to come to room temperature and
stirred overnight. The reaction mixture was neutralized and heated to 13O ⁰ G for one hour. The melting point of the polymer obtained was 22-5 ⁰ O · There were

from a solution of the polymer in D'ime thy! acetamide
Cast with a content of ψ / ο lithium chloride JFilme.
The polymer VII can be converted to polymer VI by heat treatment, the hydrazide bond being converted into an oxadiazole bond.

ÖAD ORIGINAL 909885/1578

VL

Example 9

Production of an ordered oxadiazole-benzimidazole copolymer with a structure different from the product according to Examples IV or V.

VIII + * ~ * NH

I!

CO -CH ₂ - CH ₃

1.) KOH

VIU

2.) HCl

• OH (J »rp. 368-371 * C.)

909885/1578

ORIGINAL

A mixture of 0.8O g (0.00375 mol) of 3.3 * -diamino benzidine 'and 1/16 g (0.00375 mol) of 2,5-bis- (m-carboxyphenyl) -i, 5 / ^ - oxadiazole (VIII) was during 3> 0 minutes at 220 ° C under nitrogen, then at 220 ° C under reduced pressure Pressure of about 30 mm heated for 1 hour. The received Polymer was dissolved in dimethyl sulfoxide and precipitated in water and washed with methanol. The polymer was then washed with dilute lye, rinsed with water and dried. The melting point of the polymer was above 470 ° C. A clear brown film was produced from a Solution of the polymer poured into dimethyl sulfoxide.

■ .... ■ BAD ORIGINAL

9098Ö5 / 1578 '

Claims (1)

15708; ö Claims 1 "Method for Hera toll us from heterocyclic poly" Corisates which comprise at least two different polyvalent five- and six-membered heterocyclic units with at least one heteroeleiaent consisting of N * O or S, which are arranged in the: polymeric chain in regular order, with a catch of οinea polyvalent hydrocarbon with 1 between each of the heterocyclic units switched to 15 carbon Atocen * _# lst characterized g6kennzelohnet _# dmB one substantially äqulmolar "· proportion of (A) a monomer «da * at least one · preformed · heterocyclic bond and at least two reactive ones functional · groups contains « and a conomer of (A) or (D) one monomers with at least one tonic feel funlitinnoll groups dt ucieotzt each other and the reaction to the winning dos heterocyclic polymer continues "with a · or i & ehrer" welter · heterooyolic · units are formed in the course of the reaction » 2. The method according to claim I _4, characterized in that can as monoiceres (A) 2 _# 5-bis * (p-asiinophenyl) -l _# 3 _# 4 * oxadiazole « 4-phenyl-1 # 2 »4-triazoles azole or B-Dia - {^ p-axainophenylthiaaol-Ä-yl) -benzene used New documents lArty äiAfc _S .2, .r.iSatz3desÄnderuneage3.v.4.9.] 5JÖ3 909885/1578 BAD ORIG.NAL Ί 57 υ • 3 * · 2 method according to claim 1 * characterized by ßkennzeichnot, * le. Monomoroa (B) PyroEaollithslluredieiihydrid, Diphcnyliso phthalate SobaoinoUur ©, N ^ K ^ DiphonyliisophtliÄllaiiduyloiilorid odor Bonxidin uses 4. Method according to one of claims 1 to 3 # characterized / d & A one in the weeentliohen ttquiiBol & re proportions of 2 _> 5-Bite- (p-amioophQnyl) -l, 2 _# Wxadia ^ ol and dianhydride boi «! Nor temperature of 60 ° C to -30 ° C with stirring, so did and passed and the passed product was thrown into the air. ,. ,. . . . 5) Heterocyclic .PolymersV- dadürchsge'nnze'icijnet, · '. ··. " that it comprises at least two different polyhydric 5- and ^{1 .6-;} - ^ uniform heterocyclic ■ units. with · ^ less than one hetero-,. λ element ] consisting of atas. NiO. Or S include ,,; die '-.in- regularly ¹ - • - '- ■' '-' ■. · - ·. ■■ * ■■■. . '■.;: · · "■■. ·.' ·.,. · ';' '* < · ■ "; ger, order in which: polymer chains occur, · where between .., - ■: see each of the ¹ heterocyclic ^: units, a multivalent *. :; - '.' · ■■ Hydrocarbon unit, with, '. 1' to \ 1 £ · Köhienstof f ρΐοιηβη ^ βΐη-; \ * ' 6) Heterocyciische polymers according to claim 5 »characterized in that they are repeating units of the the following formulas: 9 0 9 8 8 5/1578 BAP 1 5 7 ü b -.-; 6th -si or exhibit. 909885/1578 T) heterocyclic polymers according to claim 5 or .6, characterized in that they are blown in the form of ten 'structures', self-supporting films or fibers or threads present » 90 9885/1578