DE2019602B2 - Process for the production of moldings by molding a polymer mass from a heat-resistant N-containing polymer - Google Patents

Description

40

A common type of process for making shapes, such as foils, from a refractory Polymers consists in the fact that one soluble prepolymers with groups which under ring closure the heterocyclic Can form rings of refractory polymer in a large excess of solvent, like three to four times the amount of solvent, dissolves this solution on heated rollers or plates gives up to evaporate the solvent and a film supported by the roller or platen to form, this then peeled off the roller or the sheet and by further heating under Ring closure to the heterocyclic rings in the polymer hardens. This known method has however, the disadvantage that voids are often formed in the film when the temperature conditions should not be adjusted very carefully when the solvent evaporates. Furthermore, it is difficult peeling the uncured film off the heated roller or platen, so doing this sometimes tearing of the film due to the strong adhesion of the film to the drum or disk surface leads. Eventually, the removal and recovery of relatively large amounts of solvent occur various problems, the relatively complicated equipment and a slow throughput require.

602

In the process known from US-PS 34 28 602 and FR-PS 15 07 751, the solution of the The prepolymers are first concentrated by heating, after which the polymer mass is rolled onto a Carrier out and hardened on this in an oven by heating. Besides that this The roller-forming process can only be used for thick sheets, but the same disadvantages ·· »· ..- occur here the procedure discussed above, with Au ^ .idhme those associated with the removal and recovery of the relatively large amount of solvent are. In addition, this method has the further disadvantage that the structure and nature the surface of the molding resting on the carrier from the exposed surface differentiate and that it is very difficult to achieve evenly smooth surfaces when using rollers of the molding and that its physical properties are deteriorated.

The object on which the invention is based is therefore to use the known methods of production to improve moldings from a solvent-containing polymer composition and polymer moldings to obtain better physical properties.

The process according to the invention for producing moldings by shaping a polymer mass from a heat-resistant polymer with imid, imidazole, benzoxazole, benzimidazole, benzoxazinone, imidazopyrrolone, hydantoin, oxathiadiazole and / or oxadiazole rings and optionally groups which ring these Forming heterocyclic rings in each repeating unit of the polymer chain in an organic solvent and subsequent heating to 200 to 500 ⁰ C with evaporation of the solvent and optionally ring closure of the groups forming the heterocyclic rings is characterized in that a polymer composition is used which has 15 to 150 percent by weight, based on the weight of the heat-resistant polymer, of the organic solvent with a boiling point of at least 150 ^° C. and a heat-resistant polymer with a ring closure ratio of 15 to 100%, and which has a softening point of less than 270 ^° C., and that m deformed to this polymer mass by extrusion of the melt into a self-supporting molding.

Preference is given to using a polymer composition which is 25 to 130 percent by weight, based on the weight the heat-resistant polymer containing organic solvent, and is particularly useful the process for polymer compositions, which are a polyamideimide or a heat-resistant polymer Contain polyesterimide.

If the heterocyclic rings in the heat-resistant polymer used are A and the Groups which form these heterocyclic rings with ring closure, denoted by B in the polymer, the ring closure ratio can be expressed by the following formula:

Total number of A

-Τ- ■ 100.

Total number of B + total number of A

For example, when the heterocyclic ring in the refractory polymer is an imide ring, they are groups forming the imide ring with ring closure

Linidic acid nippen (I), amidic acid ester groups (II) the iminolactone rings (III) of the following formulas

\
C.
ι \ ^7th I.
C. \
C.
I. \ I.
C. \
C.
I.
C. C-N-R
/ I
H COOH O
Il Il
C — N — R— / I
H \ \
COOR C = N-R- 0
\ /
C.
Il Il
0

(II)

(III)

In this case, the ring closure ratio results from the total number of those contained in the molecule Imide rings, divided by the sum of the imide rings, amidic acid groups contained in the molecule, Amic acid ester groups and iminolactone rings, multiplied by 100. The amount of ring-closed Groups and non-ring-closed groups can be determined using the infrared spectrum, the NMR analysis and determined in other ways.

The above-mentioned heterocyclic groups and, if appropriate, groups which undergo ring closure forming these heterocyclic rings may be arranged regularly or randomly in the polymer be. Examples of such heat-resistant polymers are polyamide imides, polyimides, polybenzoxazoles, Polybenzimidazoles, polybenzoxazinones, polyesterimides, polyimidazopyrrolones, polyhydantoins, polyimide hydrazides, Polyoxa (thia) diazoles and copolymers thereof. When the ring closure ratio is smaller is than 15%, the application of the invention Extremely difficult process because a volatile low molecular weight compound, such as water or alcohol, forms within the molecule during ring closure.

The polymer composition used in the process of the invention must have a softening point of less than 270 ° C and even if it is heated in the extruder for less than 2 minutes, do not lose their flowability through gelling or precipitation. The softening point can be changed with Determine using the apparatus according to ASTM P 1238-57 T.

In the case of a heat-resistant polymer which, in addition to the heterocyclic rings, has polar groups, such as amide groups, ester groups, carbonyl groups or ether groups, the ring closure ratio can be relatively high and be up to 100%. In the FaHc of polymers without polar groups except the heterocyclic rings should be the ring-loop ratio be lower. For polyamides with an amide to imide ratio of more than 85:15 the ring closure ratio can be greater than 95%, and practically up to 100%. In the event that that

\ o polyamide-imide also contains ether groups or carbonyl groups, the ring closure ratio can be 100% even if the above ratio of amide to imide is even more shifted towards the imide.

Organic solvents used with preference have a boiling point of 200 ^° C. or more. Examples include N-methyl-2-pyrrolidone, Ν, Ν-dimethylacetamide, N, N - dimethylformamide, N, N-dimethylmethoxyacetamide, N - methylcaprolactam, dimethyl sulfoxide, tetramethylene urea, pyridine, dimethyl sulfone, hexamethylphosphoramide, tetramethylene sulfone, formyrene -Acetylpyrrolidone or m-cresol or p-cresol.

If the content of organic solvent in the polymer mass is below 15 percent by weight, based on the weight of the heat-resistant polymer, the polymer mass is insufficient Flowability for extrusion. With a solvent content of more than 150 percent by weight. based on the weight of the heat-resistant polymer, the molding has after extrusion insufficient dimensional stability, i.e. self-supporting properties, and there is a increased risk of voids occurring during heat treatment.

The solvent content of the polymer composition can be adjusted in such a way that the polymerization with formation of the heat-resistant polymer from the outset in the desired solution

medium amount or by first carrying out the polymerization in a larger amount of solvent carried out and removed after the polymerization part of the solvent. The polymer mass with the specified solvent content can, for example, in a finely divided state or as Granules can be processed. However, it is more convenient to carry out polymerization and extruder deformation continuously carry out and after the end of the polymerization, the resulting mixture directly in fed in the molten state to an extruder. Conventional extruders can be used for the extrusion of any type can be used. However, when the amount of solvent is particularly small, Preferably extruders with good mixing and kneading properties are used.

The moldings obtained according to the invention can have any shape and, for example, as Fibers, foils or sheets are present. The temperature used for melting in the extruder should preferably not be higher than necessary and is usually lower than the boiling point of the one used Solvent at atmospheric pressure, preferably at least 5 ° C lower than this Boiling point.

Subsequent to the extrusion, the molding is heated to 200 to 500 ⁰ C in order to remove the remaining organic solvent and, if necessary, the ring closure of the heterocyclic rings.

to effect the groups. The treatment temperature is higher than that used for extrusion Temperature. The reheating is expediently carried out in an inert gas atmosphere,

The molding is expediently after extrusion and before the subsequent heat treatment cooled to give it its dimensional stability. The cooling takes place when the temperature is at Extruding, d. H. the temperature of the extruder tool is between 350 and 30 ° C. When the molding contains a relatively large amount of solvent, is usually at the lowest possible temperature chilled. Chilled air or a liquid cooling bath can be used as the cooling medium, through which the Moldings are passed through.

Instead of cooling, the extruded moldings can also be made dimensionally stable in such a way that that they are treated with a compound which is miscible with the organic solvent and which forms the polymer does not dissolve and is liquid at room temperature. That way you can handle around when a extruded film is intended to be wound up on a metal drum without it being on the metal surface adheres. The compound which is miscible with the organic solvent can be applied to the The molding can be sprayed on, or the molding can be passed through a bath of this compound will. The contact time required for this is very short, so that one in this method is essential becomes self-supporting properties faster than with cooling. Useful for this purpose Compounds are, for example, water, aliphatic or aromatic hydrocarbons, halogenated Hydrocarbons, ketones or hydroxy hydrocarbons. Mixtures of these compounds can also be used be used. The use of water is particularly preferred, but acetone, Heptane, carbon tetrachloride, ethylene glycol or tetralin can be used. With this method should the contact between the molding and the compound which is miscible with the organic solvent not longer than necessary, otherwise there is a risk that the degree of devitrification of the polymer increases becomes and the formation loses its softness and sometimes even becomes cloudy.

In certain cases it is not necessary to use special treatment procedures to reduce the to make extruded molding self-supporting. In such cases it can cool down from the melted state Sufficient in the extruder for dimensional stability.

In the subsequent heat treatment, it is expedient to bring the molding to a certain temperature heat, which is above the temperature at which its solidification occurs, since in this way the Solvent Removal and the Ring Closure Reaction

run smoothly and quickly in the molecule.

To demonstrate the technical progress compared to known solution molding processes, a Polymer solution made from trimellitic anhydride and methylenediphenylene diisocyanate in a molar ratio of 1: 1 in N-methyl-2-pyrrolidone according to paragraph 1 of the example below? manufactured. After the completion of the polymerization, the polymer concentration became the solution adjusted to 25.0 percent by weight, d. H. to a solvent content of 300%, based on the polymer weight.

The viscosity of the solution was 1700 P at 30 ^° C. The polymer solution was poured onto a metal plate by a conventional solution molding method, and the metal plate was heated in a conventional manner using hot gas to drive off the solvent, thereby forming a film of about 50 μm Thick received. The post-heating of the film thus obtained was carried out in the same manner as indicated in Example 7 for 5 minutes by heating in a tenter-type heat treatment apparatus at 280 ⁰ C.

The physical properties were compared with those for that of Example 7 of the present invention Application received film were found.

The properties were determined according to standard methods, the comparative values are in the compiled in the following table:

Physical dimension Determination Films after Movies based on known Features method Example 7 Solution molding process toughness kg / mm ² ASTM D 882-64 T 12.7 11.5 strain % ASTM D 882-64T 22nd 22nd Resistance to bending Number of Biegevo ^r transitions JISP-8115 7500 3700 with the same film thickness Dielectric strength KV / mm ASTM D! 49-64 210 180 Cavities no Formation of a number of cavities

The inventive method in view of the relatively low solvent content in the treated polymer mass with much higher throughput rates, with the elimination of a Bubble formation in the molds and without the difficulty of recovering large amounts of solvent work. The equipment required is relatively simple and the design is simple exact, as it takes place in the molten state. The inventive method is mainly used for Used in the manufacture of polymer films, but can also be used in the manufacture of fibers or thicker ones Moldings are used.

The viscosity given in the following examples is determined as follows

Natural logarithm (F ₂ -F ₁ )

where F _{2 is} the expiration time of the solution, F _{1 is} the expiration time of the solvent and C is the concentration of the polymer in the solution in grams of polymer each

100 ml of solution means. The usual viscosity shows a value, measured at 30 ^° C., of 0.5 g / 100 ml of N-methyl-2-pyrrolidone.

The R.S. used in the following examples means the percentage by weight of solvent based on the weight of the polymer; d. H.

Solvent (weight)

R. b. = ——: -rr —— 'IUU.

Polymer (weight)

example 1

Samples of a polymer prepared as described below mixed with N-methyl-2-pyrrolidone in an amount, based on the weight of the polymer, of 8.13, 21, 58, 67, 80, 100, 135 and 155% were too small Processed lumps and fed to an extruder with a diameter of 20 mm, which was heated ^{to 180 0 C.} A 150 mm wide film-forming spinneret was attached to the mouthpiece of the extruder, and this was also heated to 180 ° C. When the sample was fed with a solvent concentration of 8%, the product exiting the spinneret did not have a good film condition. Then, when materials with solvent concentrations of 21, 58, 67, 80,100 and 135% were melt extruded, they resulted in extrusion from the spinneret

no problem. Finally, if the sample with a solvent concentration of 155% was extruded in the melt, the moldings flowed and could not keep their shape.

Films, which were obtained from the samples with solvent concentrations from 21 to 135%, were added directly to a heated at 200 ⁰ C metal strip and 2 minutes at 300 ⁰ C, 3 min at 25O ⁰ C and 3 minutes at 300 ° C heated to give tough, light brown films. The ring closure ratios within the molecules of these films were approximately 100%. These films had no melting points, but they started to decompose when heated to a temperature above 350 ° C. They had tensile strengths of 11.6 kg and elongations of 13%, indicating excellent heat resistance.

The polymer samples identified above were prepared as follows:

In 289 parts of N - methyl - 2 - pyrrolidone were

234.2 parts of butane - 1,2,3,4 - tetracarboxylic acid and

198.3 parts of 4,4'-diaminodiphenylmethane dissolved. The resulting solution was stirred and heated to 200 ⁰ C. From time to time N-methyl-2-pyrrolidone and water were added in an amount corresponding to the amount distilled off. The viscous solution obtained after 4 hours contained a high molecular weight polymer according to an infrared spectrum and had the following structure.

-N

CO-CH, CH ₂ -CO

CO-CH-CH

HOOC-CH ₂ CH ₂ -COOH HNOC-CH-CH-CONH

The ring closure ratio within the molecules of this high molecular weight polymer was 85%. The solution was concentrated to the sample concentrations indicated above.

Example 2

An appropriately the information provided later produced solvent-containing polymer having a solution viscosity at 250 ° C of more than 5000 P, a polymer content of 50% and a cyclization ratio of 85% was continuously fed to a small extruder at a temperature of 200 ⁰ C, of 190 ⁰ C was heated, extruded in the melt and with the help of a spinneret, which was also ^{heated to 195 0} C, formed into a film. The film emerging from the spinneret was heated with the aid of a hot air dryer which was heated to 250 ° C. in order to remove a larger part of the solvent. Thereafter, the film was placed in a tenter-type heat treatment apparatus heated to 300 ° C. and heated under tension.

The film obtained was tough and yellowish brown, had a strength of 14.6 kg / mm ² , an elongation of 14.8% and a folding strength (thickness 50 μ) of 1600 times. The polymer referred to above was produced as follows:

A three-necked flask fitted with a stirrer and nitrogen inlet was charged with 68.486 parts of N, N'-diethoxycarbonyl -4,4'-diaminodiphenylmethane, 38.424 parts of trimellitic anhydride and 200 parts of N-methylpyrrolidone, and the contents of the flask were kept at for about 2 hours 195 to 200 ⁰ C stirred.

Example3

A polymer solution according to the following specifications prepared, the polymer had a cyclization ratio of 96%, was concentrated at 18O ⁰ C and then continuously fed to a small heated to 190 ⁰ C extruder, extruded in de melt and by means of a spinneret which is also at 190 ⁰ C, was deformed into a fi n. The molten film exiting the spinneret contained 93% solvent. After it had been cooled with the aid of a casting drum, it was continuously introduced into a tenter-like heat treatment apparatus which was heated to a temperature of 260 to 320 ° C., and the ring closure was completed by heat treatment. The film obtained had a strength of 15.1 kg / mm ² , an elongation of 12% and a tensile strength (thickness 50 μm) of 11,000 times.

509521/3;

The polymer solution used as the starting material was prepared as follows:

In 250 parts of tetrahydrofuran were dissolved 38.42 parts of trimellitic anhydride, the solution was cooled to 0 ⁰ C, and then 19.83 parts of solid 4,4'-diaminodiphenylmethane were portionwise added.

After the mixture had been reacted for 2 hours at 0 to 10 C, 44.4 parts of dicyclo-

hexylcarbodiimide dissolved in 500 parts of tetrahydrofuran was added dropwise. The reaction temperature in the system was kept at 0 to 10 ^{° C.} After the resulting mixture was reacted for 10 hours at 20 ⁰ C, the reaction product was filtered to obtain to remove dicyclohexylurea and so Diiminolactondicarbonsäure the following formula

HOOC

COOH

29.1 parts of this compound were dissolved in 200 parts of N-methyl-2-pyrrolidone. 12.51 parts of solid diphenylmethane diisocyanate were added to the resulting solution, and the mixture was ^{heated to 180 °} C. for 5 hours and gave a viscous polymer solution.

Example 4

A highly viscous polymer solution (Ringscblußverhältnis 85%) was continuously fed to a small, heated to 190 ⁰ C extruder, and with the aid of a likewise heated to 190 ⁰ C spinneret, the polymer was melt-extruded and shaped into a film. The soft film that came out of the spinneret in a molten state was transferred directly to a metal belt heated to 200 ° C., the temperature of which was gradually increased, and heated to 310 ° C. for 5 minutes. The film obtained in this way was tough and brown and had strength of 16.5 kg / mm ² and an elongation of 18.5%.

The polymer solution used as the starting material was obtained as follows:

Using 25 parts of N-methylpyrrolidone 8.008 parts of 4,4'-diphenyl ether diamine were used as the solvent and 7.324iile bis (trimellitic anhydride) anhydride stirred at room temperature for 30 minutes, and then stirred while Was heated to 190 ° C for 5 hours.

Example 5

Polymer particles with 32% N-methylpyrrolidone, and a ring closure ratio of 75% were fed in a small spinning machine, spun at 19O ⁰ C in the melt and air-cooled. Thereafter, the solidified filaments were wound around a heating roll, and heated to 300 ⁰ C. The threads obtained were somewhat brown and firm.

The solvent-containing polymer particles were obtained as follows:

One made from butanetetracarboxylic acid and 4,4'-diaminodiphenyl ether polymer solution obtained in N-methylpyrrolidone with a polymer concentration of 50% was heated to 80 ° C. under reduced pressure

and concentrated to adjust the solvent concentration to 32%. The obtained polymer was pulverized into a finely divided material.

Example 6

A virtually solvent-free polymer with a cyclization ratio of 33% wurdeals supplied to such a heated at 170 ⁰ C extruder, and it tried to extrude in the melt. However, the polymer did not melt and extrusion did not go well. Subsequently, the finely divided polymer was allowed to stand in the vapor of N-methylpyrrolidone to allow it to penetrate into the particles, so that the solvent concentration became 23%. Even then, the particles still looked dry. When these particles were fed into a heated to 17O ⁰ C extruder and extruded in the melt, they melted and were simply using a -Spinndüse, which had likewise been heated to 170 ° C, deformed into a film. When this molten film was ^{wound around a metal drum cooled to 20 °} C. to be cooled and solidified, a light yellowish excellent film was obtained. This film was soluble in N-methylpyrrolidone, and when it was ^{heated to a temperature higher than 120 °} C., it softened. This film was introduced into a tenter type heat treatment apparatus, from both surfaces het heated such that the temperature of the film was 280 to 300 ⁰ C by means of radiant heaters, and etwj

Treated in the heat for 6 minutes. The preserved folk possessed a ring closure ratio in the molecule of 100%, was yellowish and tough, insoluble in an organic Solvent and had no melting point. Sii had a tensile strength of 12 kg / m / deh of 42%. Even if they were kept at 180 ° (in an atmosphere for a long time, they fell no significant changes in physical] properties, and the film showed excellent Heat resistance

The polymer used as the starting material was prepared as follows:

Trimellitic acid was found in N-methylpyrrolidone Chloride and 4,4'-diaminodiphenylmethane polymer

sized to a solution of the following polyamideimide precursor mixture to obtain:

After suspending this solution in a poor methanol-water type solvent, reprecipitated the polymer using a large amount of water, filtered and dried to obtain a finely divided polymer which hardly contained any organic solvent.

Example 7

The solution of a polymer having high molecular weight, a solvent concentration of about 50%, a viscosity in N-methylpyrrolidone at 30 ° C of 1.3 and a ring closure ratio of imide rings within the molecule of 72% was fed continuously to a heated to 14O ⁰ C Extruder , heated to 140 ° C and extruded in the melt to a film-like state from a spinneret heated to 150 ° C. The film coming from the spinneret was wound up around a metal drum cooled to 20 ° C. and thus cooled and solidified, continuously introduced into a tenter-type heat treatment apparatus which was heated to 280 ° C., and heat treated therein for about 5 minutes. The obtained film was dark brown, had an imide ring closure ratio of about 100% and had no melting point.

This film had a tensile strength of 12.7 kg / mm ² , an elongation of 22%, and even when it was ^{treated in air at 250 °} C. for 10 hours, there was no substantial change in physical properties and it was excellent

ίο heat resistance.

The polymer solution referred to above was obtained as follows:

Trimellitic anhydride and methylenediphenylene diisocyanate were heated in a molar ratio of 1: 1 in N-methylpyrrolidone and with evolution of carbon dioxide polymerized to give a very viscous solution.

Example 8

A polymer solution obtained in accordance with the following information was heated to 170.degree heated extruder fed, extruded in the melt and formed into a film. After the out the film coming from the spinneret for cooling and

Ϊ5 fastening has been wound around a cooling drum it was heated to 100 ° C in hot air for 5 minutes.

The film obtained was transparent and somewhat yellowish and also tough.

The polymer solution was obtained as follows:

By polymerizing isophthalic acid dihydrazide and pyromellitic anhydride in N-methylpyrrolidone a solution of a mixture of precursors represented by the following formula was obtained can. The ring closure ratio in the molecule was 60%.

OC CONH NH · CO COOH

N / A

HOOC CONH NH -

CO CO

OC CONH N T I! N-NH-

Λ / N AA /

co co

X /

This solution was concentrated under reduced pressure at 7O ⁰ C, to adjust the solvent concentration to 92%.

Example 9

A solution of a polymer with high molecular weight, an inherent viscosity in a concentration of 0.5, obtained by copolymerizing 4,4'-diaminodiphenylmethane, pyromeffitic dianhydride, trimellitic acid and isophthalic acid chloride in a molar ratio of 3: 1: 1: 1: 1 in N-methylpyrrolidone % in N-methylpyrrolidone at 30 ° C of 0.80 and a concentration ratio of 52% was concentrated under reduced pressure to bring the solvent concentration to 77%. The concentrated solution was ^{fed to an extruder heated to 140 °} C. with a diameter of 30 mm, extruded in the melt and processed into a film ^{with the aid of a spinneret heated to 150 ° C.} After the thin film coming out of the spinneret ^{had been wound up around a metal drum cooled to -10 0} C in order to be cooled and solidified, the film was first preheated with a hot air dryer heated to 200 ° C, then continuously in a tenter-like heat treatment apparatus which was heated to 280 ⁰ C, introduced and heated under tensile stress darii. The film obtained was tough and yellowish brown, had an interlocking ratio in the molecule of 100 ° / and had no melting point.

Example 10

A polymer produced according to the later information was given as such a temperature of 170 ° C A heated extruder was fed in and an attempt was made to spin it in the melt. The polymer melted

But not, and the experiment was negative. The finely divided polymer was then left to stand in N-methylpyrrolidone vapor so that it could penetrate up to a concentration of 23%. Even then, the particles didn't feel particularly moist, but rather dry. They were fed to an extruder heated to 170 ° C. and extruded in the melt. They melted easily and emerged in the form of a film from a T-shaped mouthpiece, which was also heated to 170 ° C. This film was slightly yellowish, soluble in N-MethylpyrroHdon and softened upon heating to a temperature higher than 120 ⁰ C. This mixture was heated to 17O ⁰ C film was introduced into a tenter type heat treatment apparatus, heated from both sides by radiant heater and heated for about 6 minutes in such a way that the film temperature was 280 to 300 ⁰ C. In this case, the heat treatment was carried out by first heating without tension, and as the removal of the solvent proceeded, tension was gradually applied. The obtained film had a ring closure ratio in the molecule of 100%, was yellowish and tough, insoluble in organic solvents and had no melting point. It had a tensile strength of 12 kg / mn and an elongation of 42%. ^{Even when it was heated to 180 °} C. in air for a long time, there were no significant changes in physical properties, which shows excellent heat resistance. The polymer used as the starting material was prepared as follows.

In N-methylpyrrolidone, 4-chloroformyl

Phthalic anhydride and 4,4'-diaminodiphenylmethane polymerized to form a solution of a polyamideimide precursor mixture of the following structure:

IO

HOOC

After suspending this solution in a poor solvent, methanol and water became Using a large amount of water the polymer reprecipitated and filtered to a finely divided Obtain polymer which hardly contained organic solvent. The ring closure ratio in the molecule of this polymer was 33%.

Example U

One by polymerizing dihydrazide isophthalate and pyromellitic anhydride in N-Methy'.pyrrojo lidon obtained solution of a polymer of the general formula

OC CONH • NH • CO

HOOC

COOH

CONH - NH

OC

CONH · N

CO

CO CO

N-NH-

CO

and with a ring closure ratio of 60%, it was concentrated by heating to 70 ° C under reduced pressure to make the concentration of the solvent 45%. The polymer was then processed into a small lump, which was ^{fed to an extruder heated to 170 °} C. and then extruded in the melt to form a film. The film coming out of the spinneret was immediately heated to 300 ° C. in hot air for 5 minutes. The film obtained was transparent, somewhat yellowish and tough.

Example 12

A solution prepared according to the following instructions of a polymer having high molecular weight, a solvent concentration of about 50%, an intrinsic viscosity in N-methylpyrrolidone at 30 ⁰ C of 1.3 and a Imidringschlußverhältnis of 72% was continuously under heating at 140 ⁰ C a to 14O ⁰ C heated extruder so fed and extruded in the melt with the aid of a heated to 150 ° C spinneret. The film emerging from the spinneret was transferred directly to a metal belt in an inert atmosphere and heated to 280 ° C. for about 5 minutes. The film obtained was yellowish brown, had a Imidringschlußverhältnis of about 100%, had no melting point, and had a softening point of 280 ⁰ C. The film had a tensile strength of 12.7 kg / mm ^2, an elongation of 22%, and even when they was heated in air at 250 ° C for 10 hours, no significant changes in physical properties occurred, indicating good heat resistance. showed.

The polymer 6s used as starting material solution was obtained as follows:

Trimellitic anhydride and methylenediphenylene diisocyanate were in a molar ratio of 1: 1 in N-methylpyrrolidone with carbon dioxide evolution

ment polymerized, a very viscous solution was obtained.

Example 13

Polymer carvings produced as indicated below were fed to an extruder with a diameter of 45 mm, heated to 175 ° C., and extruded in the melt with the aid of a screw whose groove depth gradually decreased. A T-like spinneret provided at the end of the extruder was also ^{heated to 175 °} C. and had a width of 300 mm and a mouthpiece slot of 0.5 mm. The polymer extruded from the spinneret in a film-like state was wound around a rotating cooling drum which was attached directly below the spinneret, where the polymer was continuously cooled to 20 ° C. and then continuously stirred into a tenter-like heat treatment apparatus. The inside of this heat treatment apparatus was heated to 330 ° C. by hot air. After the film was subjected to the heat treatment while both ends in the film width direction were held by clamps for about 10 minutes, the film coming out of the tenter was wound up after its both ends were cut off in the film width direction. The film obtained had a thickness of about 50 μm and was a tough, brownish polyamide-imide film. Some of the physical properties of this film are summarized below:

lithic anhydride added. After the mixture was continuously stirred for 1.5 hours at 17O ⁰ C, to give a very viscous polymer. This polymer had a solvent content of 60%. the ring closure ratio was 95% and the intrinsic viscosity 0.70. When the polymer was cooled to room temperature, it solidified. This solid was crushed into polymer chips.

Example 14

properties Measured
value Measurement method Tensile strength 10.6 kg / mm ² ASTM D 882-64 T strain 23% ASTM D 882-64T Breakthrough
strength
Dielectric 182 KV / mm ASTM D 149-64 constant 4.5 ASTM D150-64T (1 KC, 25 ° C) Dielectric Loss factor 0.0067 ASTM D150-64T Pyrolysis off transition temperature 450'C TGA (in air) density 1.37 Density gradient Folding strength Pipe method (50 μ thickness) 8700 times JISP-8115

A polymer solution according to the following data obtained was concentrated under reduced pressure, the solvent concentration to bring to 60%, the concentrated solution was fed to a heated to 100 ° C extruder, extruded in the melt and a heated at 170 ⁰ C spinneret at a Deformed film.

The thin film emerging from the mouthpiece was continuously put into a tenter-type heat treatment apparatus introduced, which was heated to 280 ° C, and heated under tension. The received Foil was yellowish brown, tough and flexible.

The polymer solution mentioned at the beginning was obtained as follows:

In N-methylpyrrolidone there was 384 parts of trimellitic anhydride and 482 parts of 4-amino-4'-carboxybiphenyl ketone reacted at 190C for 3 hours. to the adduct thus obtained was added 901 parts of p-phenylene diisocyanate and 192 parts of trimellitic anhydride added. The mixture was reacted at 170 ° C. for 1 hour and at 210 ° C. for 30 minutes to form a polymer solution with an inherent viscosity of 0.81 (ring closure ratio 97%).

Example 15

The polymer chips were produced as follows:

In 250 parts of N-methylpyrrolidone, 105 parts of trimellitic anhydride were dissolved, and 75 parts of solid p-aminobenzoic acid were added to the resulting solution. The mixture was ^{heated to 200 °} C. for 2 hours and stirred. Water generated during the reaction was distilled off, and the moisture content at the end was 120 ppm. 250 parts of 4,4'-diphenylmethane isocyanate and 86 parts of Trimel were added to this solution (in a sludge state) C. continuously fed into an extruder heated to 175 ° C. and extruded into a film-like structure with the aid of a spinneret heated to 175 ° C. The film emerging from the spinneret was applied to a metal drum cooled to 20 ° C., then cooled and solidified and continuously fed into a tenter heat treatment apparatus heated to 210 "C and heated for about 5 minutes. The film obtained was brown and flexible. It had a tensile strength of 10.2 kg / mm ² , an elongation of 16.5% and a folding strength of 5800 times. Even when this film was treated in air at 250 ° C for 10 hours, no substantial change in physical properties occurred and the film had good heat resistance.

The polymer solution mentioned at the beginning was obtained as follows:

In N-methylpiperidone there was 482 parts of 1,4,5-naphthalenetricarboxylic anhydride and 274 parts of m-aminobenzoic acid reacted at 190 to 200 ° C for 4 hours.

954 parts of N, N'-dimethoxycarbonyl-4,4'-diaminodiphenyl ether and were added to the reaction product 166 parts of isophthalic acid were added. The mixture was polymerized at 190 ° C for 2 hours.

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17th
Example 16

HO

A polymer solution prepared as described below was concentrated under reduced pressure to obtain samples having solvent concentrations (based on the weight of the polymer) of 40, 55, 137 and 155%. All of these samples were solid at room temperature (only the sample with the solvent concentration of 155% was not completely solid). These samples were finely pulverized, and then the particles obtained were ^{fed to an extruder heated to 160 to 180 °} C. with a diameter of 20 mm and shaped by extrusion (the mouthpiece had a 150 mm wide slot for forming a film). In the extruder deformation, the sample with the solvent concentration of 155% was poor in dimensional stability, and the extrusion of this sample from the spinneret was not smooth. However, the remaining samples were able to retain their shape and extrude smoothly. The extruded samples were transferred to a metal belt, cooled to room temperature, and peeled from the belt, but except for the sample with the solvent content of 40%, the peeling of the remaining samples was not easy and did not proceed smoothly as the amount of the solvent increased, and in the case of the sample with a solvent concentration of 137%, peeling was very difficult. Therefore, a water bath having a temperature of 30 ° C. was installed 10 cm below the extruder barrel, and extruder molding was carried out so that the extruded product was wound up on a drum after being immersed in this water bath. As a result, from the sample having the solvent concentration of 137%, a film having self-supporting properties was obtained without destroying the shape of the extruded product. When the film was peeled off from the drum around which the film was wound, it was again confirmed that the peeling could be easily performed without any problem, and the film could be continuously subjected to subsequent heat treatment. Now they w- xn

ίο samples with 55 and 137% solvent heated for 2 minutes at 200 ⁰ C for 3 minutes at 250 ⁰ C and 3 Minutsn to 300 ° C, thereby to obtain tough, light brown film. The ring closure ratios in the molecules were about 100%. The films had no melting points, but when the films were heated to a temperature higher than 350 ° C, they began to decompose. They had tensile strengths of 14 to 16 kg / mm ² and elongations of 28 to 32%. When the films were brought into contact with water, their surface became somewhat white and opaque, but when heated, the color disappeared and the surfaces became transparent again.

The polymer solution used as the starting material was prepared as follows:

Ir. 650 g of N-methylpyrrolidone were 234 g of butane-1,2,3,4-tetracarboxylic acid and 198 g of 4,4'-diaminodiphenylmethane dissolved. The solution obtained was stirred and heated to 200 ° C. The N-methylpyrrolidone distilling off with water during this time was replaced from time to time. A polymer solution obtained after 4 hours was a mixture of compounds high molecular weight of the following structures as confirmed by infrared analysis. The ring closure ratio of the polymer was 85%.

HN

CO-CH ₂ CH ₂ -CO

CO-CH-CH CO

HOOC-CH ₂ CH ₂ -COOH

HNOC - CH - CH - CONH

Example 17

At 180 ° C a polymer solution according to the following information prepared was continuously fed to a small, heated to 190 ⁰ C extruder and extruded using a heated at 190 ⁰ C in the spinneret of the melt into a film. The solvent concentration was 150%, the molten film coming out of the spinneret was introduced into water and obtained self-supporting properties. Immediately thereafter, the film was preheated in a hot air dryer heated to 220 ° C. and then continuously introduced into a tenter-type heat treatment apparatus in order to achieve complete solvent removal and ring closure treatment.

The film obtained had a tensile strength wedge of 16.2 kg / mm ² , an elongation of 18% and a folding strength (thickness 50 μ) of 1450 times.

The polymer solution mentioned at the beginning was prepared as follows:

In 250 parts of tetrahydrofuran, 38 parts of trimellitic anhydride were dissolved, the resulting solution was cooled to 0 ⁰ C, and then 20 parts of 4,4'-diaminodiphenylmethane were added in portions in solid state.

After the resulting mixture was ^{reacted at 0 to 10 °} C. for 2 hours, 44 parts of dicyclohexylcarbodiimide dissolved in 500 parts of tetrahydrofuran were added dropwise to the reaction product. The reaction temperature in the system was kept at 0 to 10 ^{° C.} After the reaction product had been reacted for 10 hours, the resulting reaction product was filtered to remove di-

19th

remove cyclohexylurea and diminolactone dicarboxylic acid of the formula

HOOC

COOH

to obtain. In 200 parts of N-methyl-2-pyrrolidone 29 parts of Düminolactondicarbonsäure were dissolved, to the resulting solution 12.5 parts of solid Diphenvlmethandiisocyanat were added, and by heating the mixture for 5 hours? .Uf 180 ⁰ C it was a viscous polymer solution.

Claims (3)

20 2 claims: 1. Process for the production of moldings by shaping a polymer mass from a heat-resistant polymer with imid-j imidazole, benzoxazole, benzimidazole, benzoxazmon, imidazopyrrolone, hydantoin, oxathiadiazole and / or oxadiazole rings and optionally groups which, with ring closure, these heterocyclic rings Form rings, in each repeating unit of the polymer chain, in an organic solvent and subsequent heating to 200 to 500 ⁰ C with evaporation of the solvent and optionally ring closure of the groups forming the heterocyclic rings, characterized in that a polymer composition is used which is 15 to 150 percent by weight, based on the weight of the heat-resistant polymer, of the organic solvent with a boiling point of at least 15O ⁰ C and a heat-resistant polymer with a ring closure ratio of 15 to 100%, and which has a softening point of less than 270 ⁰ C, and that one this polymer mass d Formed into a self-supporting molding by extrusion of the melt. 2. The method according to claim 1, characterized in that a polymer mass is used, the 25 to 130 percent by weight, based on the weight of the heat-resistant polymer, des contains organic solvent. 3. The method according to claim 1 or 2, characterized in that a polymer mass is used, which contains a polyamideimide or polyesterimide as a heat-resistant polymer.