DE1595723A1 - Process for the production of nitrogen-containing polymers - Google Patents

Description

1 River Röad, i3cheneotady 5, New York (V. St, A.).

Process for the production of nitrogen-containing polymers

The invention relates to a method for producing nitrogen-containing polymers, namely 1) polyhydroxyamides (hereinafter referred to as "polyamides" for the sake of brevity), consisting of recurring units of the formula

-R-G-IH

and 2) alkali salts of these polyamides (hereinafter referred to as "Alkali polyamides"), the repeating units

the formula

II)

contain, in which H is a divalent radical of the formula

_p , - / ~ \ - or

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- ά -

is, Z for an alkali metal atom (e.g. sodium, potassium, Cesium etc.), A is a divalent radical of the formula OO

- σ -, -S-, (. * ch _o ->, - O - or -ORS .- it <- P «-

where R »is methyl or phenyl, m is an integer of more than 300 (ζ · Β. 50-10,000 or more), η the number 0 or 1, ρ is an integer from 1-8 and q is the number 0 or 1, and wherein the individual bonds of A are in the p-position to the amino and hydroxyl groups or, in the case of the alkali salts, to the oxygen atoms. In formula II and in other formulas for alkali salts of the polyamides, the hydrogen atoms are fat atoms (H) and the alkali metal atoms (Z) are only bound to oxygen atoms that are directly bound to the benzene rings.

The process for making the aforementioned polyamides and alkali polyamides are characterized in that, in the case of the polyamides, amino compounds of the formula

HO

OH

with diaoyl halides of the formula

0 0

^ Ii? R ■ ■

17) X-O-R-C-X

converts, where A, R, m and η have the meanings mentioned and X is a halogen, e.g., chlorine, bromine or fluorine. The procedure for the preparation of the alkali polyamides is characterized in that the polyamides of the formula I in an alkali ' hydroxyl solution and thereby one or more hydroxyl groups of the polyamide substituted by an alkali metal atom "

The polyamides of the formula I can advantageously be used under

3toff on increased "

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exclusion of oxygen to elevated temperatures of. 200-400 ° ö

-BAD ORKSSNAL

■ - 3 -

are heated, whereby ring closure takes place and polybenzoxazoles of the formula

-R-

wherein R ₉ A ₁ η and η have the meanings mentioned, are obtained · ·

By treating the alkali polyamides with aqueous mineral acids such as hydrochloric acid and sulfuric acid polyamides of the formula I can in turn be obtained.

Bb is SU note that the remainder A with its carbon

wle

Carbon bonds or similar carbon-carbon bonds between the two phenyl nuclei in formula I, where η is Hull, not in o-position to the nitrogen .or Oxygen atoms may stand, but in p-position to Amino group or to the nitrogen atom or in the p-position to the Hydroxyl group or to the oxygen atom. In the case of polybenaoxazoles of the formula Y, the individual bonds are e.g. the carbon-carbon bonds of group A in p-position to at least one of the heteroatoms of the benzoxazole rings · »

Aliphatic polybenzoxazoles, which are made up of repeating units of the formula

consist »whereBP is a divalent aliphatic radical, are described in U.S. Patent 2,904,537 " According to this patent, the aliphatic polybenzoxazole directly as a result of the reaction of an aliphatic carboxylic acid

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group formed with a Hydroxyaminephenylgruppe in. der the hydroxyl and amino groups are attached to adjacent carbon atoms of a benzene ring, which in turn form a Ability to form a benzoxazole ring «Another possibility an aminohydroxyphenylalkanoic acid can be condensed with itself, or one can condense bis-hydroxyaminophenyl compounds and make carboxylic acids. In this case, however, the reaction proceeds directly to the polybenzoxazole form without an intermediate compound, as is to be found, for example, in formula I above. This has the consequence that it is not possible to take advantage of processability, which is given by the use of aqueous solutions. Aromatic polybenzoxazoles (e.g. those in French patent 1,365,114) for the most part relatively high-melting solids and practically insoluble in common solvents, when they are made by the direct process described in the aforesaid French patent. The usefulness of these polymers is severely limited by the fact that they are essentially non-formable.

Surprisingly, it has been found that it is possible To produce intermediate polyamides, which are in many common solvents, such as dimethylacetamide, dimethyl sulfoxide, K-methyl-2-pyrrolidone, etc., are soluble «which is equally important is, these polyamides can optionally be heated to achieve ring closure and formation of the polybenzoxazoles. In addition, aqueous alkali salt solutions of the polyamides can be used that can be extruded into acidic media to make films, fibers, etc., and the products obtained in this way can be converted into the polybenzoxazole form by heating to elevated temperatures will. This "thus offers the possibility of foils and fibers of extremely good ϊ / heat resistance, which in are insoluble in most organic solvents.

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The polyamides according to the invention advantageously be carried, manufactured by reacting diaryl compounds of the formula III with Diaoylhalogeniden of formula .iy · Compounds of formula III which can be used for the preparation of the polyamides include, for example, 3 »3 ^f -Dihyäroxybenzidin, 3.4 * -D] amino-3 ^f , 4-dihydroxybiphenyl, 3 »3 M) iamino ~ 4» 4 • -dihydroxydiphenyl, 2,2-bis (3-amino-4-hydroxyphenyl) propane ^ 3,3 '-> diamino- 4,4'-dihydroxydiphenylsulfone, 1,4-bis (3 ^ amino-4-hydroxyphenyl) -n-butane, 3 » 3 ^f - * diamino-4» 4 »-dihydroxybenzophenone, 2,2-diphenyl- <2, 2-bis (3-amino-4-hydroxyphenyl) ethane, 3.3 ^{liters of} diamino, 4.4 ^{liters of} dihydroxydiphenyl ether. Suitable acyl compounds of the formula IV are, for example, terephthaloyl chloride, isophthaloylochloride, terephthaloyl bromide, malonylochloride, suooinylohloride, adipylohloride, suberylochloride, sebacyl chloride, etc.

In the preparation of the polyamides, it is advantageous to use solvents in which the two reactants mentioned are both soluble. Suitable solvents are, for example, N ^ '- dimethylacetamide, IT-methylpyrrolidone and !!, H'-dimethylformamide. Examples of suitable acceptors for hydrogen halides are dimethylacetamide, JT-methylpyrrolidone, N, N ¹ -tetramethylurea and hexamethylphosphoric acid amide. In addition to being acceptors for hydrogen halides, these materials can also be used as solvents. * Other suitable acceptors for hydrogen halides are, for example, pyridine, tributylamine, triamylamine, ghinoline, β- and γ-piolinines and the lutidines Aoyl compound must generally be reacted in essentially equimolar concentrations. This initial reaction of the benzidine compound and the acyl compound leads to the formation of the polyaaid structure of formula I. A slight excess.

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up to about 5 Μο1- $ ί of one respondent over the other is not excluded. It was found that a slight molar excess of the aoyl compound leads to slightly lighter colored products. Reaction temperatures of about -30 to 150 ⁰ O or higher are suitable for the purpose. Excessively high reaction temperatures must be avoided in order to keep oxazole ring formation to a minimum.

If the polyamide structure of formula I is obtained by reacting the amino compound with the diamond halide, heating this polyamide derivative to temperatures of about 200-35O ⁰ C or higher, preferably in the absence of oxygen, results in cyclization and formation of the benzoxazole rings. When the isophthaloyl or terephthaloyl chlorides with dihydroxydiaminobiphenyls are used to produce the polyamides, the polybenzoxazoles formed in this way are infusible and insoluble in practically all organic solvents.

Formula I polyamides have many uses. They are at increased! Temperatures e ± aa * k, have good tensile strength, and many are flexible at room temperature. Pick up some polyamides that are crystalline and hence the option offer an improvement in the properties through orientation by cold stretching, these polyamides with their free Hydroxyl groups in alkaline materials, e.g. in aqueous solutions of tetrabutylammonium hydroxide, sodium hydroxide, Potassium hydroxide, cesium hydroxide, etc. can be dissolved to form water-soluble polymers. The aqueous alkaline Solutions of these polymers can then be extruded into a medium that causes the polyamide to precipitate will. For example, you can extrude a sodium hydroxide solution of the polyamide in sulfuric acid depending on the applied extrusion method, foils, fibers etc. can easily be obtained »

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To produce these alkaline solutions, e.g. aqueous alkali hydroxide solutions, aqueous 0.01 to 2n alkali solutions can be used. The polyamide can be used in an amount of 0.001-0.2 parts by weight per part by weight The preferred concentration of this alkaline solution and the weight ratio of the latter to the polyamide are different depending on factors such as the type of used alkaline material, the molecular weight of the polyamide, the application in question, etc. By combining the Polyamides with alkaline solutions can be obtained from polymers made up of repeating units similar to those for formula I are composed with the exception that one or more of the hydroxyl groups in the polyamide by one -OZ radical are substituted, where Z is the remainder of the alkaline Material such as alkali metal, e.g., sodium, potassium, cesium and lithium is an example of a polyamide in which some of the hydroxyl groups are substituted by an -OZ radical is a polymer made up of repeating units

η 0

0

.Hq -Z

2-q

consists, in which A, Z, m, η and q have the meanings mentioned and the average number of alkali metal atoms in the polymer containing the above repeating unit is about 0.05-2 per repeating unit. In other words, the proportion of hydroxyl groups in the polymer that have been substituted by alkali metal atoms, can be 2-1005 *. It is obvious that with that Polymer that consists of repeating units of the formula YI, both hydroxyl groups in each repeating

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Unit can be replaced by a —OZ residue Mtoen or a Hydroxyl group is substituted by an -OZ radical. Finally, there can be a number of repeating units of the formula I are present in which no -OZ radicals are present, but these units with units of the formula VI, in which one or both hydroxyl groups have been replaced by an -OZ radical, are copolymerized.

The above-mentioned aqueous alkali hydroxide solutions can be used as spinning solutions for the production of fibers or foils · This is usually done in such a way that, the abovementioned aqueous alkali metal hydroxide solutions are placed in an acidic medium, e.g. introduces aqueous Ο »1 to 6N hydrochloric acid, sulfuric acid, etc., using enough acid to neutralize virtually all of the base in the solution, and all of it originally to regenerate existing hydroxyl groups. The treatment with these acidic solutions (which advantageously contain buffer salts) converts the fibers or foils into the polyyanide structures of the formula X, and these fibers or foils can be easily isolated (e.g. by heating to remove the liquid phase) and with the formation of strong, Tough foils or fibers can be oriented · These can then be extruded or spun oriented Products are heated to elevated temperatures in the manner already described, causing cyclization and formation the benzoxazole rings is effected. When the polybenzoxazole film or fiber is composed of a dihydroxydiaminobiphenyl and a Terephthaloyl or isophthaloyl halide are derived the films and fibers produced in this way are essentially infusible and insoluble. If, on the other hand, the initial Reactants derived from an aliphatic aoyl reactant such as adipyl chloride and the benzidine are, the resulting films or fibers (in the polybenzoxazole state) are sohraeläbar and soluble. Tough and strong films can also be cast from the alkali metal of the polyamide

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will. These foils can be converted into polyamide derivatives by treatment with acids.

The polybenzoxazoles of the formula T are used ala & itz · - resistant coatings for a wide variety of materials and as insulation for electrical conductors * For example, the polyamide can be dissolved in a suitable solvent, * .B. I-methyl-2-pyrrolidone, in concentrations of clay O ₉ 1-20 percent by weight or more, based on the total weight of the solution, dissolved and applied to electrical conductors such as copper, copper alloys, aluminum, etc., then applied the polyamide insulation can be heated to elevated temperatures »whereby the polybenzoxazole compound is formed from recurring units of the formula Y. These conductors with insulation can be bent around a mandrel of the same diameter as the conductor without any evidence of cracking or soldering of the insulation.

Polybenzoxaiol made from the polyamide «are extreme tough, have high softening temperatures (300 ° or more) and excellent resistance to hydrolysis and weather influences. Due to these properties, the polybenzoxazoles are ideal as slot sol-ation in engines. Films made from polybenzoxaseols can also be used where resistance to heat, moisture, etc. is important · fibers made from polyamide and polybenzoxazole can be used for the production of fabrics and fabrics which must have high heat resistance.

The polyamides of formula I have intrinsic viscosity clay at least 0.1 and advantageously clay about 0.25-3.5, sat at 25 ⁰ in H-methyl-2-pyrrolidone. In this respect, according to the invention, molecular weights (determined by measurements on the basis of the osmotic pressure) in the range from 10,000 to well over 1,000,000 can be obtained.

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BATH ORIGINAL)

- · 10 -

would do τοη »more than O ₁ 5 (measured in sulfuric acid) and usually in the range τοη 0.75-5.0 or above ·

In the following examples, all parts are by weight. If analytical values are given, the percentages in brackets are the theoretical percentages for the Elements.

Production τοη 3.3'-I) ihydroxybengidine

3,3'-Dihydroxybeniidine was prepared by reacting τοη 3i3 ^f -WÄe * h ~ oxybenzidine with 57jfcLger Jodwasaeretoffäure after the experience τοη Burkhardt and Wood (J.Ohem.Soo «, 151 (1929). The production of this connection is also in patent specification 2,497,248. The crude product was recrystallized under nitrogen from a dimethylaoetamide water emisoh and washed with ethyl alcohol. The purified product was dried well. Duroh aisles above 270 ⁰ O! replaced it sioh Compound was identified as 3,3 ^I -dihydroxybenzidine.

Production τοη 3.3'-Diamino · ^ .4'-dihydroxybiphenyl .

A solution of 15 g (0.08 hol) 4,4 »-dihydroxybiphenyl in 810 ml acetic ^{acid was added dropwise at 70 0} O with 10.14 ml (0.16 hol) concentrated nitric acid. The solution turned darker and red in color, and orange crystals soon began to appear. Bas mixture was Hinuten 30 at its boiling point τοη 118 ⁰ O kept and filtered after cooling * The precipitation was separated, gewasoneη with acetic acid and dried to obtain 15.3 g of 3 ^»l 3 ^dinitro-l -dihydroxyhiphenyl 4F4, rom melting point 284- 285 ⁰ O were obtained, a solution τοη 5 g of the nitrated biphenyl in about 125 ml pyridine .wurde ⁱ in a Paar-SchüttelTorrichtung using τοη platinum oxide as a catalyst at 120 ⁰ O · The hydrogen uptake was fast and practically quantitative filtered, the pyrldine removed by heating and the booth boiled with ethanol, the

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desired 3,3'-Diamino obtained dihydroxybiphenyl ^, ^4> "This material was further purified by dissolving in diethylacetamide and treatment with AktiTkohle * Haoh addition τοη hot water sum filtrate the diamino compound described above was obtained, the melting point of about 300 ⁰ Analysis to identify this compound was found to contain 66.3 * C (66.7 *), 5.4 * H (5.6 *) and 12.8 * K (13.0 *).

Production of 2.2 "-Bie (3-anino-4-hydroxyphenyl) propane

About 5 al (0.08 hol) of concentrated nitric acid, which was diluted with 1.6 ml of water and 15 ml of acetic acid, were added at a temperature of 14-16 ⁰ O to a solution of 9.0 g (0.04 hol) 2,2-Biβ (4-hydroxyphenyl) propane "in 60 ml of cold acetic acid the mixture was stirred for 30 Hinuten at about Bäumteaperatur (25-28 ⁰ O)" laughing cooling the mixture below room temperature, a precipitate was obtained, washed and was recrystallized from acetic acid to give 2,2-bis (3-nitro-4-hydroxyphenyl) propane, melting point 134.5-135.0 ° C. The identity of this compound was confirmed by analysis, which revealed that it was 56.5 * f <56.6 *) contained 0, 4.5 * (4.4 *) H and 8.6 * (8.8 *) H. A solution of 1.6 g of this nitro compound in 250 ml of absolute alcohol was hydrogenated at tree temperature in a Paariohüttelvorriohtung using 0.1 g of platinum oxide as a catalyst until the theoretical amount of hydrogen had been absorbed. The ethanol solution was heated and the catalyst was filtered off Xthanol solution, crystals with a melting point of 258-261 ⁰ O were obtained. After two TJmkriatallieation from absolute ethanol, a product was obtained which was identified by analysis as the diamino compound mentioned above, the following analytical values were obtained: 68.8 * (69.7 *) C , 7.1 * (7.0 *) H, 9.8 * (10.9 *) ».

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BATH ORIGINAL

' Production of 3 «3 ^f -Dlaalno-4t4 ^t: -dihydroxydiphenyliulfoB

About 25 g (0.10 mol) of 4.4 ^t ~ dihydroxydiphenyl sulfone suspended in 80 ml of water were treated with 120 ml of nitric acid. After heating on the steam bath for 3 hours, a yellow product was separated, washed in hot water and then boiled in a small Äthanolmenge * After TJmkristallisation from Ithanol 3.3 ^I dinitro-4,4 ^I was -dihydroxydiphenyleulfon of melting point 238,5-24O ⁰ O · Bine obtained solution of 6.8 g of the dinitroaromatic sulfone in 80 ml of pyridine was Hydrogenated in a pair of shakers using platinum oxide as a catalyst. Hydrogen was added first at room temperature and then at 115 ⁰ C, to 95 * of the theoretical amount had been consumed · The Pyrldinlösung was evaporated to dryness and the residue taken up in methanol and treated by addition of a little water twice with activated carbon. After Umkristalllsation from a methanol-water Gemisoh the above besohriebene 3 '3'-diamino-4,4'-dihydroxydiphenyleulfon obtained from Sohmelepunkt 238 to 238.5 ⁰ O. The identity of this compound was confirmed by the analysis which showed that it contained 50.79t (51.4 *) 0, 4.4 * (4.3 *) H and 9.5 * (10.0 *) N ·

example 1

A solution of 2.05 g (0.0101 mol) of redistilled isophaloylochloride in 20 ml of retistilled Ν, Ν-dimethylacetamide, prepared under nitrogen, was immediately converted into a solution of 2.16 g (0.0100 mol) of recrystallized 3.3 « -Dihydroxybenzidine given in 20 ml of dimethylaoetamide. An additional 5 ml of dimethylacetamide was used to rinse any residue of the isojtthaloyl chloride solution into the reaction mixture. After the mixture had been held for about 1 hour under nitrogen and with stirring at room temperature (about 25-27 ⁰ C), the difference Semiseheβ at slow addition of 1 1 of rapidly stirred methanol from a polymer. The polymer was filtered off, washed all over with 1 l of hot methanol, filtered and dried in the air. The product resulted in sioh

BATH ORIGINAL

here a polyamide with recurring units of the formula

where m has a value greater than 30. The polymer had an intrinsic viscosity of 0.81 as measured in N-methylpyrrolidone. The analysis of the polymer revealed that it consisted of the repeating units shown above. A 7-IOjfcLge solution of this polyamide in N-methylpyrrolidone was used to cast films to flexible at temperatures of 50-100 ⁰ G.

About 2.5 grams of the polyamide (about 14.5 milli-equivalents an.Hydroxylgruppen) according to Example 1 were dissolved in 50 ml of an aqueous solution containing 0.6 g of sodium hydroxide (15 milliequivalents Base) contained ^ being an aqueous solution of the Polyamide was obtained in which essentially every hydroxyl group was obtained was converted into a -ONa group, so that the polymer consisted essentially of recurring units of the following formula:

-KH-

8th.

ONa

; .0Na

A sample of this solution was spread on a flat surface and the water evaporated. A flexible film was obtained which had a tensile strength of 1175 kg / cm and an elongation of 16 ° C. This film was then immersed in an aqueous Salzaäurelöaung containing enough HCl to neutralize the total sodium, genotomen · _f out to remove any acid residues washed with water and dried again. This polie, which in a poly.

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-H-

was more converted wraä-e? that from the structural units of the Formula VII passed, it was then tested for physical properties It had a tensile strength of 1235 kg / cm and an elongation of Hy * the foil was then under Nitrogen held at 300 ° 0 for 3 hours, whereupon it was converted to the polybenzoxazole form, which was made from recurring Units of Formula VIII shown below in Example 2 consisted of «This film had a tensile strength of 1385 kg / cm and an elongation of 11 ^

Example 2

The conversion of the polyamide prepared according to Example 1 in the polybenzoxazole, which is made up of repeating units of the formula

existed, was carried out as follows: A 10 # Lge solution of the polyamide according to Example 1 was formed in H-methylpyrrolidone, a copper wire was passed through the solution and the coated wire was then heated to about 300 ⁰ O, with a flexible, firm on the wire Adhesive, extremely heat-resistant insulating film was formed from a polybenzoxazole of the formula VIII A film of the polyamide according to example i can also be kept under nitrogen for 30 minutes at 300 ^° C., a film of the corresponding polybenzoxazole being formed, which consists of recurring units of the formula VIII.

Example 3

I'm a mixture of. 0.954 g (0.003 mole) of 3 '3 ^f -Dihydroxybenzidin and 0.649 g (0.003 mol) was stirred for about 6 Diphenylieophthalat Hinuten at about 250 ⁰ O under nitrogen. The volatile materials boiling up to 300 ⁰ O were distilled off,

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whereupon it was heated for a further 10 minutes to a temperature of 40O ⁰ O · The total reaction time was about 27 minutes · The resulting yellow polymer was cooled, whereby a pol jixozoxazole compound with recurring structural units of the formula VIII was obtained * This polymer was in insoluble hot or cold K-methylpyrrolidone, diphenyl ether, dimethyl sulfoxide and dimethylaoetamide,

Example 4

A solution of 2.05 g (0.0101 mol) of isophthaloylochloride in 20 ml of dimethylaoetamide was added to a solution of 2.16 g (0.10 mol) of 3,3'-dihydroxybenzitine in 20 ml of dimethylaoetamide. The mixture was added under nitrogen was stirred, immediate polymerization took place, recognizable by a clear increase in viscosity and development of heat, by which the temperature was raised to about 60 ° 0 · The viscous solution was left to stand for about 1 hour, whereupon a polymer made up of repeating units of the formula VII was insulated. Films cast from the solution were flexible, transparent and looked. The polymer was isolated from the beacon mixture by pouring it into 1 liter of rapidly stirred acetone. The polymer was filtered off, washed several times with hot methanol, filtered again and dried. Us had a viscosity of 0.81 in H-methylpyrrolidone. Ba was soluble in concentrated sulfuric acid, concentrated sodium hydroxide, hexamethylphosphoramide and in dimethyl sulphide. If 100 parts of a 1 molar aqueous hydroxide solution were mixed with 4 parts of this polyamide, the resulting solution could be worked into films or fibers by extruding it into a dilute aqueous acid solution. The analysis of the poly was as follows: 63.6jC (69.5 *) 0.1.1 % (4.08 «*) H, JT. The Xnfratoanalysis also confirmed that the combination of recurring units of the formula VII ^nd 009818/1630

BATH ORIGINAL

Example 5

A polyamide similar to that of the formula YII of Example 1 was prepared as follows. 100 ml of N-methylpyrrolidone was added to a mixture of 6.48 g of 3,3'-dihydroxybenzidine and 6.12 g of isophthaloyl chloride. The mixture was stirred for about 16 hours, after which the polymer thus formed was isolated by precipitation with 1 l of methanol, washed well with hot methanol, filtered and dried. Here, too, a polyamide of the formula VII was obtained. The analysis of this compound showed that it was 66.4 * (69.5 *) C, 4.8 * (4.08 *) H and 7.9 * (8, 09) contained N. A sample of this polyamide * was converted to the polybenzoxazole of Formula VIII by holding it at 340-355 ⁰ O for one hour under a vacuum of 0.001 mm Hg. The yellow polybenzoxazole obtained, which also ^{did not melt at 600 0} O, was insoluble in hot or cold dimethyl sulfoxide, N-methylpyrrolidone, dimethylacetamide and hexamethylphosphoramide. However, it was soluble in cold concentrated sulfuric acid. According to analysis, the polymer contained 76.3 * (77.5 *) 0.3.9 * (3.2 *) H and 9.0 * (9.04 *) V · The infrared spectrum of this polymer indicated that it was the aforementioned polybenzoxazole. This polybenzoxazole is remarkably resistant to decomposition at elevated temperatures and does not ^{melt even at 60O 0 O «}

The cyclization of the polyamide, which contains recurring units of formula VII, to give the polybenzoxazole can also be carried out using polyphosphoric acid. For example, 0.25 g of the polyamide obtained according to Example 1 was kept in 11.9 g of polyphosphoric acid (115%) at 130 ^° C. for 16 hours. The resulting clear, viscous solution was cooled to room temperature and added to 50 ml of ice water, whereby the polymer was precipitated. The resulting mixture was boiled, cooled, filtered, washed with water and methanol and dried to give the desired polybenzoxazole

Example 6

This example describes a method for insulating electrical conductors with a polyamide which consists of repeating units of the formula VII. The polyamide produced according to Example 4 was converted into a solution by dissolving 1.5 g of this polymer in 20 ml of N-methylpyrrolidone. A copper wire and a nickel-plated copper conductor were coated with the solution by dewing the conductors twice in the solution, to get two layers on the wires. Each Sohicht was maintained for 3 minutes at 300-35O ⁰ C, thereby obtaining the polybenzoxazole insulated conductors. The insulation on both conductors was pliable when the conductors were bent around a mandrel that was the same diameter as the wire. The insulation showed no thermal ^{shock after 1 hour at 250 0} O and had a push-through temperature of about 4-2O ⁰ G. These tests are described in TJ.SA patent 2 936 296.

Example 7

A mixture of 2.16 g (0.01 mol) of 3,3'-dihydroxybenzidine and Added 2.05 g (0.010 t mol) of tereptthaloyl chloride. To this Gemisoh was given 50 ml of dimethyl acetamide. Naoh misshap of the constituents, a reaction took place immediately, developing considerable heat and producing a yellow polymer was precipitated from the reaction mixture. To the reaction mixture 1 liter of methanol was added to wash the polymer. The polymer was filtered off, twice with 500 ml of methanol each time washed and dried. The product obtained was a polyamide composed of recurring units of the formula

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existed in which m has a value greater than 30. This Polymer was soluble in concentrated sulfuric acid at room temperature. A 10? C solution of the polymer in 1N sodium hydroxide was viscous. From this solution of the polymeric NatriurasA-üzes were made by pouring and evaporating the water immediately tough films made · This alkali polyamide consists of repeating units of the formula

H.

where m and q have the meanings mentioned. Foils and fibers were produced from the basic viscous solution, by extruding the solution directly into 10% sulfuric acid (the sodium salt being converted into that of sodium atoms fräie polyamide was converted). The films and fibers were washed and dried. The fibers, which were still moist were oriented by stretching and then dried. Hereby strong oriented fibers were obtained

Example 8

A solution of 1.08 g (0.005 mol) of 3.3 ^f -diamino-4,4- ^l -dihydroxydiphenyl in 10 ml of dimethylacetamides was converted into a solution of 1.08 g (0.00513 mol) of isophthaloyl chloride in 10 ml Dimethylaoetamide added. After stirring the constituents (with a further 5 ml of dimethylaoetamide being added), polymerization took place immediately, recognizable by the development of heat and an increase in viscosity. After standing for 1.8 hours to ensure completion of the reaction, the polymer was isolated by precipitation with methanol and washed twice with methanol. In this way, a polymer composed of repeating units of the formula was obtained

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I ν /

consisted »in which a has the meaning already mentioned. This polymer would have an intrinsic viscosity of 0.34 in N-methyl 1-pyrrolidone at 25 ⁰ * The analysis showed that the polymer was 63.2 * (69.5 *) 4.5 * (4.8 * ) H and 7.3 * (8.09 *) N. The infrared analysis confirmed that it was the desired polyamide "

Example 9

To a cooled to -15 ⁰ C solution of 2.583 g (0.01 mol) of 2,2-Bie (3-amino-4-hydroxyphenyl) propane (prepared in the manner described above) in 20 ml of N-methylpyrrolidone, under the Nitrogen was maintained, 2.03 g (0.01 mol) of isophthaloyl chloride were added. The temperature of the exothermic reaction mixture was kept at 10 ⁰ O by means of a cooling system. The solution was stirred for 1 hour at about 10 ° C. and then for 62 hours at Left to stand at room temperature. In this way, a solution was obtained which contained a polymer composed of repeating structural units of the

consisted of where m is an integer greater than 30 · This solution could be spread out on a flat surface and the solvent is evaporated. This was a strong one.

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get supple film. Analysis of this polymer, which had an intrinsic viscosity of 0.50 in N-methylpyrrolidone at 25 ⁰ O, showed that it was 68.55 * (71.1 ° / *) 0.5.3 * (5.2 #) H and 6 | 9? G (7.2j <) N. By heating this polymer for a period of about 1 hour to about 300.degree. C. in the absence of oxygen, a polybenzoxazole bond with recurring units of the formula

received, in which m has the meaning already mentioned · This Surprisingly, polybenzoxazole was soluble in Eresol In contrast to the previously described Polybenzoxaeolen, which are not soluble in this solvent and in the usual Solvents were practically insoluble »alkali salts of the polyamides of the formula XII could be used to produce films and fibers made from recurring units of the Formula XII passed, being extruded into acidic solutions. By heating to elevated temperatures, heat-resistant Polybeneoxazole fibers and films are obtained.

Example 10

To a cooled to -15 ⁰ under nitrogen and G retained solution of 2.583 g (0.01 Hol) 2,2-bis (3-amino-4-hydroxyphenyl) propane in 20 ml of H-IIethylpyrrolidon 2.03 g ( 0.01 mol) Terephthaloylehlorid given «The temperature of the exothermic reacting mixture was kept at 10 ⁰ O by a cooling bath. The mixture was ^{stirred for 1 hour at 10 0} O and then for about 62 hours at room temperature, whereby a polymer was obtained repeating units of the formula

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XIV)

HO

where m is an integer greater than 30. Dieees polymers, daa had an intrinsic viscosity of 0.50 in N-methylpyrrolidone, could be used in the form of a solution in N-methylpyrrolidone for casting films which Evaporation of the solvent were tough and pliable. When this polymer was heated for approximately 1 hour at 300 ⁰ G in the absence of oxygen, the polybenzoxazole, consisting of repeating units of the formula formed

σ (0Ή ₃ ) ₂ -

F ^ J— _N -

existed, in which m has the meaning mentioned, In contrast to the polybenzoxazoles prepared according to Example 2, 3 and 5, which were relatively insoluble (except, for example, in sulfuric acid), that was according to this example manufactured polybenzoxazole in cresol löelioh. On the In the manner described in Example 9, from alkali salts of the polyamides of the formula XIV, polybenzoxazole films and fibers are produced.

Example 11

A solution of 0.987 g (0.0049 mol) of isophthaloyl chloride in 10 ml of dimethylacetamide was added at room temperature to a solution of 1.361 g (0.0049 mol) of 3,3 * -diainino-4 »4 ^l -dihydric xydiphenylsulfone (prepared on the manner described above) in 10 ml of dimethylacetamide. The entire remaining isophthaloylochloride solution was rinsed into the reaction mixture with 5 ml of dimethylacetamide. After stirring the ingredients

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a solution of the polymer was obtained in water precipitated, separated, washed and dried · This polymer, which consists of repeating units of the Structural formula

existed, in which m is an integer greater than 30, had an intrinsic viscosity of 0.16 in N-methyl-2-pyrrolidone at 25 ⁰ O. The infrared analysis confirmed the identity of this polyamide. The polymer had an exceptionally high heat resistance, evident from the fact that it could be kept 64 hours without any noticeable change in the properties at 300 ⁰ G, Polybenzoxasolfasern and sheets, consisting of recurring units of the formula

β—

existed, in which m has the meaning already mentioned, could from alkali salts of the polyamide of the formula XVl the manner described in Example 9 can be prepared.

Example 12

A solution of 1.8 g (0.0102 mol) of adipylochloride in 10 ml of dimethylaoetamide was added to a solution of 2.16 g (0.01 mol) of 3.3 ^{I-dihydroxybenzidine in 20 μl of dimethylaoetainide under nitrogen.} When the mixture was stirred, polymerization took place immediately, recognizable by the development of heat and a sharp increase in viscosity of the reaction mixture,

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The solution was stirred at room temperature for about 2 hours. Subsequently, a part of the solution duroh casting and evaporating the solvent at 75 ⁰ O was processed into a tough, gesohmeidigen film. The polyamide was isolated by precipitation with 1 l of methanol. The precipitate was washed twice with methanol, filtered and dried to give a polymer which was insoluble in hot or cold N-methyl-2-pyrrolidone, dimethylacetamide, cresol and formic acid. However, the polymer was soluble in 1N-sodium hydroxide, cold sulfuric acid, and hot dimethyl sulfoxide. The intrinsic viscosity of the polymer was 1.21, measured in sulfuric acid at 25 ⁰ O * Analysis of this polymer showed that it was 64 »1 pounds (66,4-Ji) 0, 5.7 pounds (5> 5 pounds) H and Contained 8.3 pounds (8.6jC) N. The infrared spectrum of the polymer confirmed that it was the polyamide *, made up of repeating units of the formula

- (OH ₂ ) ₄ 8 -

existed, In which m has the meaning already mentioned · The polymer of the formula XTIII was dissolved in sodium hydroxide solution to form an extremely viscous solution. By extruding this solution in to sulfuric acid solution, films and fibers were obtained which were extremely strong after washing with water, orientation and drying. A sample of the polyamide consisting of recurring structural units of the formula I7III, was converted to the polybenzoxazole by being heated in nitrogen at 200-300 ⁰ C. That the cerium level had been reached was indicated by the fact that there had been a weight loss by water removal of 10.5 pounds compared to the theoretical loss of 11. OjC. This polybenzoxazole consisted of again

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recurring structural units of the formula

where m has the meaning already mentioned. On the in Example 9 described manner could from the alkali salt of this polyamide of the formula XTIII polybenzoxazole fibers and - films are produced

It is obvious to those skilled in the art that in addition to the amino compounds of the formula III and the diaoyl halides of the formula IV, the experiments described in the table below were used, as well as other amino compounds or diacyl halides, for the purposes of the invention for the preparation of the Polyamides can be used without departing from the scope of the invention. Many examples of these other participants in the reaction were genaiint in the description · Likewise the conditions under which these reactions are carried out can be varied within wide limits, as has also already been mentioned · the admixture of Fillers («.Β. Carbon black, silicon dioxide, etc.), dyes, Pigments and the like to the polymers are not excluded.

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Claims (3)

Pat e a t claims 1. Process for the preparation of polyamides with recurring units of the formula (2-9) in which R is a radical of the formula or A is a divalent radical of the formula It (-CHp-), - 0 - or - ( where R ^{1 is} a methyl or phenyl radical and ρ is a number v6n 1 to 8, and in which Z is an alkali metal ion and η is zero or 1 ·, m is a number greater than j50 and q is 0, 1 or 2 and in uer'cler "radical A is in ■ p-eteTluhg to the nitrogen or oxygen atoms, dadur.ch denotes that one diamines of the formula A. OH II with diacyl halides of the formula O tr O η in which X is a halogen atom and R has the meaning mentioned, and optionally reacting the polyamides obtained with alkali metal hydroxides. 1595? P 2. Process for the production of farm bodies, daäurclj characterized in that polyamides of the formula I, in which q is zero or 1, are converted into an aqueous, acidic one Medium extruded. . - 3. Process for the production of polybenzoxazoles, thereby characterized in that polyamides of the formula I in which q is 2, optionally after the previous Deformation, heated to temperatures of 200 to 400 ° C with exclusion of oxygen. 009818/1630