PL82355B1 - - Google Patents

Description

The proprietor of the patent: E. I. Du Pont de Nemours and Company Wilmington, Delaware (United States of America) Manufacturing of fibers or films from polyamides. Am. No. 3,414,645 is known to use a wet method with a dry nozzle, in which a solution of purely aromatic polyamides is extruded through a gaseous medium into a coagulating bath, then stretched in a washing liquid, rinsed, dried and stretched hot German Federal Patent Specification No. 1810,426 describes some optically anisotropic carbocyclic aromatic polyamides blends which, when used as a raw material in the wet process, make it possible to obtain fibers having good strength immediately after advance. it is without stretching or heating. It has been found that while treating the fibers at higher temperatures increases the strength of the fibers, heating may adversely affect certain properties of the fibers used for some purposes. The heating of the fibers increases their crystallinity and, in general, reduces toughness and elongation at break. The heated fibers may become brittle, which reduces their useful value as a raw material for the production of a cord for vehicle tires. 20 polyamide fibers and foils which, immediately after advance, ie not further processed, have a tensile strength much higher than that of fibers or foils obtained from the same polymer by known methods. Namely, the fibers produced according to the invention have a tensile strength of at least 18 g / denier, an elongation at break of at least 3.5%, their original apparent crystallite size is less than 52 A, and their radial orientation is expressed as The crosswise ordering of the crystallite, hereinafter referred to as L.CO, is at least 10. The tensile strength of these fibers is 0.40-1.5 g / denier or more, and the modulus of elasticity is 300-800 g / dec. According to the invention, polyamide fibers and films are produced by extruding the mixture through nozzles into a layer of inert, non-coagulating liquid and then into a coagulating bath. This blend comprises a polyamide of formula 1, where R is a divalent radical and n is a number 0 or 1, of formula 2, where R 'is a divalent radical. and the group of formula III, in which R "is a bivalent radical, where if in the polyamide there are groups of formulas 1 and 2, then they occur in equimolar amounts, and at least 95 mol% of the total 823,553 82355 4 of the amount of R radicals, R 'and R ", which are the same or different, constitute single, advanced bonded rigid radicals, or a series of such rigid radicals linked directly to each other by overlying bond, wherein the rigid ring radicals may be linked by azo groups or by groups azoxy. Sulfuric acid in a concentration of at least 98% by weight, sulfuryl chloride, sulfuryl fluoride or mixtures thereof is used as the solvent according to the invention. A feature of the process according to the invention is that a solution of polyamide in the solvent is used. concentration (C) of at least 30 g and preferably 40-56 g per 100 ml of solvent, and the intrinsic viscosity of the polyamide is at least 2.0 but not less than 2.8-0.05 at a concentration of 30 g / 100 ml of solvent. The mixture used in the process according to the invention has a preferably solid consistency at a temperature of 25 ° C. and turns out at a temperature of 40-120 ° C., preferably at a temperature of 70-90 ° C. For the production of fibers according to the invention, in a vertical section, Fig. 2 shows a fiber cross-section, Figs. 3, 4, 5 and 8 show graphs of electron deflection on a selected area of the fiber cross-section, the gaps being broken. have the lowest photographic density, and in gaps shown by solid lines the thickness of the lines is proportional to the photographic density, Figs. 7 and 10 show full and half-deflection densitometric plots, and Figs. 8 and 9 show parts of densitometric plots. In the apparatus shown in FIG. 1, pre-separating mass is pumped through line 51 through pre-extermination head 52, nozzle openings 53 and gas layer 55 into coagulation liquid 56 in pre-separating tube 60 through which the formed fibers 54 are routed. A thick bundle 65 with a plurality of freshly advancing fibers is guided under a guide roller 57 and wound onto a rotating coil 59. Coagulating fluid 56 flows from reservoir 61 through pre-chamber 60 to a second reservoir 62, from which it is returned to the first reservoir 61 by means of pump 63 and pipe 64. As mentioned above, the fibers or films of the invention consist of a polyamide containing essentially only repeating groups of the formulas 1, 2 or 3. wherein R, R ', R "and n have the meaning given above, wherein the radicals R, R' and R" consist of a single rigid radical with an advanced bond or a number of such radicals joined by these bonds. In addition, two rigid ring radicals can be linked by azo or azoxy groups. Thus, the polymer consists of polyamide or polyoxyamide units, when n in formula 1 is zero, forming rigid chains. of the copolyamide, that is, when R or R 'is a mixture of at least two different radicals, or when all the groups of the above formulas are present in the polyamide, have an elongation of at least 4.5% / t, while the fibers or films made of from a homopolyamide have an elongation of at least 3.5%. The term "rigid" as used above means (a) ring radicals, namely single or fused multi-ring aromatic carbocyclic or heterocyclic radicals, trans-1-, 4- cyclohexylene of formula 4 and 1,4 [2,2,2] dicyclooctylene radicals and (b) linear unsaturated radicals such as vinylene radicals —CH = CH— and ethynylene radicals —C = C—. containing amino groups bonded directly to linear unsaturated radicals are not permanent, therefore vinylene or ethynylene radicals cannot constitute the R 'radical or that part of the R "radical which is linked to the" NH "group in formula III. The term "overhang" denotes those chain bonds of a radical which are substantially coaxially extended, such as, for example, in the p-phenylene radical of the formula V, or in parallel, such as, for example, in the 1,5-naphthylene radical of the formula 6 or in the radical trans-1,4-cyclohexylene, and directed in opposite directions. Polymers of this structure, mixed with certain strongly acidic solvents, also have the ability to form anisotropic or liquid crystalline phases. This phenomenon is described in detail below. Particularly preferably R, R 'and R "represent radicals such as trans-1,4-cyclohexylene, 1,4-phenylene, 1,5-naphthylene, 2,6-naphthyllene radicals. of formula 7, 2,5-pyridylene of formula 8, 4,4-diphenylene of formula 9, trans, trans-4,4'-dicyclohexylene of formula 10 and 1,4-phenylene radicals linked by radicals trans-vinylene or ethynylene, azo or azoxyl groups In addition, R in formula I may preferably represent a trans-vinylene, ethynylene, trans, trans-1,4-butadienylene radical of formula 11 or 2,4'-trans-vinylene-phenylene. of formula 12, the last of the mentioned radicals may also be the radical R "in formula 3. The radicals R, R 'and R" may contain substituents, preferably non-reactive, e.g. under the influence of heat, during further processing of the polymer , for example, in the case of thermal treatment of products obtained from these polymers. The reactivity is undesirable, as cross-linking of the polymer could take place. u, resulting in undesirable changes in the pre-intersection weight and / or the fibers. Such non-reactive substituents are, for example, halogens such as chlorine, bromine and fluorine, lower alkyl radicals such as methyl, ethyl and isopropyl radicals, methoxy, cyano and nitro groups. In general, it is preferred that one radical contains no more than two, especially no more than one substituent. It is also preferred that no more than 20 * / of all R, R 'and R "substituents in the polymer are in the form of substituted radicals R". Polyamides (n being the number 1) where R and R 'represent 1,4-phenylene, 4,4'-diphenylene, 2,6-naphthylene, 1,5-naphthyl radicals are particularly preferably used as polymers. - new and trans-1,4-cyclohexylene, and in addition R is 2,5-pyridylene or trans-vinyllene, R "is 1,4-phenylene and at least 50 mole% of the total amount of R and R are aromatic radicals. Particular preference is given to using polymers in which R is 1,4-phenylene, 4,4'-diphenylene, 2,6-naphthylene, 2,5-pyridylene, trans 1,4-cyclohexylene and trans-vinylene, R 'represents the trans-1,4-cyclohexylene, 1,4-phenylene radical and mixtures containing the 1,4-phenylene radical and up to 50 mole% of the radical 4,4'- - diphenylene and R " is 1,4-phenylene radical, where at least 75% by mole of the sum of R and R 'radicals are completely aromatic and at least 75% by mole of R or R' radicals are 1,4-phenyl radicals Linear. The chains of the linear condensation polymers used in the process of the present invention may contain up to about 5 mole percent radicals not meeting the conditions described above, for example, having no protruding bonds or being rigid. Of course, such radicals have various effects on the properties of the raw product, that is, directly after it is not subjected to any further treatment. For example, rigid radicals such as the m-phenylene radical, in which the bonds extending from the chain are neither coaxial nor parallel, directed in opposite directions, as well as highly flexible radicals such as the hexomethylene and tethylene radicals, can be used in small amounts, while radicals such as the 4,4'-dubenylene radical can be used in greater amounts, for example above 25%, and the fibers according to the invention from such blends also have the desired properties. While this is not preferred, a small number of amide units in the linear condensation polymer chain may be replaced by other non-amide-forming stable species, such as ester, ureas or sulfonamides. However, these products are generally more difficult to manufacture and their scope of application is more limited. The polymerizing process according to the invention may be a homopolymer, any copolymer, an ordered copolymer, or a mixture of homopolymers and / or copolymers having the characteristics described above. The fibers or membranes of the invention may contain known additives for analogous processes, for example dyes, fillers, anti-shine substances, UV light fixers, antioxidants, etc. such polyamides as: poly (p-phenyleneterephthalic acid amide), hereinafter referred to as PPD-T, poly (p-phenylene-p, p'-diphenyl dicarboxylic acid amide), poly (p-phenylene-1,5 amide) -naphthalene dicarboxylic acid /, trans-4,4'-dodecahydride diphenylene phthalic acid /, poly (trans--1,4-einnamic acid amide), amide / p-phenylene-4,8-quinoline dicarboxylic acid , 1,4- [2,2,2] -diycyclooctylene terephthalic acid polyamide, p-phenylene-4,4'-azoxybenzene-dicarboxylic acid amide copolymer and terephthalic acid amide, p-phenylene acid polyamide copolymer 4,4'-trans-stilbene dicarboxylic acid / and poly (p-phenylenacetylene dicarboxylic acid amide) The polymers used in the process according to the invention are preferably prepared by reacting the corresponding monomers in the presence of an amide-type solvent. The reactions are carried out at low temperature, for example, as described in US Pat. 20 Am No. 3,063,966. In order to obtain polymers with a high molecular weight, the monomers and the solvent should contain as little impurities as possible and the water content of the reaction mixture should be less than 0.03% by weight. p-phenyleneterephthalic acid amide is preferably prepared by dissolving 1,728 parts of p-phenylenediamine in a mixture of 15,200 parts of phosphoric acid hexamethylamide and 30,400 parts of 30 N-methylpyrrolidone, cooling the solution to 15 ° C in a polymerization reactor in an atmosphere. nitrogen sphere and, with vigorous stirring, add 3243 parts of Terephthaloyl Chloride Powder. The solution turns into a gel and takes the form of dry lumps within 3–4 minutes. The mixture is then stirred for 1 1/2 hours, possibly by cooling, to keep the temperature of the mixture "around 25 ° C. The polymerization reaction is essentially quantitative and the reaction mixture contains 7.5% of a polymer with an internal viscosity of around 5.5. This viscosity can be controlled by adjusting the monomer to solvent ratio, if instead of the monomer to solvent ratio of 9.83% used in the above example, a monomer of 8.64% is used, then the reaction mixture contains 6 5% of a polymer with an internal viscosity of 6.0, while when using about 11.7% of monomer, the mixture contains 9.0% of a polymer with a viscosity of 2.5. The resulting acidic product with a lumpy consistency is mixed or ground with water in a colloid mill, such as the Waring Blendor system, then drain the polymer, rinse by mixing with soft water to remove the solvent and hydrochloric acid, and then drain. The rinsing and draining process is repeated about 4 times and finally the product is washed with distilled water. In order to facilitate the neutralization process, water containing sodium carbonate or sodium hydroxide can be used for one of the rinses. The resulting polymer is dried at a temperature of 120 to 140 ° C. The polymerization process can also be carried out by continuously mixing the polymers. Sulfuric acid having a concentration of at least 9%, sulfuryl chloride, sulfuryl fluoride or mixtures of these acids are preferably used as solvents in the process according to the invention. Sulfuric acid with a concentration greater than 100% can also be used, i.e. fuming sulfuric acid, but sulfuric acid with a concentration of about 99.8% is most preferably used, because at higher concentrations the presence of excess sulfur trioxide causes decomposition of the polymer and a reduction in its internal viscosity, which may reduce the breaking strength of the fibers. The extent of this decomposition depends on the time and temperature of the reaction, so if fuming sulfuric acid is used, the reaction at elevated temperature should be as short as possible. In addition to the solvents mentioned above, other solvents, such as hydrofluoric acid, may also be used. halogenated alkyl sulfonic acids, halogenated aromatic sulfonic acids, halogenated acetic acid, halogenated lower alkanols, halogenated ketones or aldehydes. This additive may constitute up to 30% by weight of the total amount of solvents together with the additive, the amount of these additives depending on the type. solvent and polymer. If sulfuryl fluoride is used instead of sulfuric acid or a lower polymer concentration is used, then a greater amount of the above-mentioned additives can be used. In general, the higher the percentage of halogen in the additive, the more additive can be used without causing phase separation. used in a 1: 1 weight ratio with sulfuric acid, chloride and sulfuryl fluoride. Sulfones, chlorinated phenols and nitrobenzene may be used in addition to the solvent in amounts less than those mentioned above. The water content of the mixture used as a starting product according to the invention should be carefully regulated so that it is less than 2,000 because the excess water is may make it difficult to receive. the dissolution of the permeable mixture as well as the cause of polymer decomposition. A relatively dry polymer, preferably containing less than 6% water, should be mixed with an anhydrous solvent under conditions that reduce the effect of atmospheric moisture, and the resulting mixture should be stored in a dry atmosphere. In order to avoid decomposition of the polymer and to obtain a less viscous product, the mixture should be kept in a liquid state during the batch process as low as possible and heating to temperatures above 90 ° C must be kept to a minimum. It is particularly advantageous to prepare the pre-mass continuously and feed it directly to the processing nozzles, since the storage time of the mass is thus shortened. If the process is carried out batchwise and the pre-quenching mass is stored for later use, it can be cooled and solidified, preferably in an atmosphere of dry nitrogen. Before use, the mass is comminuted into granules or powder and directed to a melting screw device feeding pre-chamber nozzles. The concentration (C) of the pre-mixture mass is determined in grams of polymer per 100 ml of solvent at 25 ° C, with sulfuric acid being the solvent. and optionally another solvent added. In the process according to the invention, a mass of at least 30 and preferably 40 g of polymer per 100 ml of solvent should be used, which when using sulfuric acid as solvent is about 98-100% t, corresponding to the polymer content in a weight of at least 14, preferably 18% by weight. Preference is given to using masses containing 40-56 g of poly (p-phenyleneterephthalic acid amide) per 100 ml of acid with an intrinsic viscosity of at least 3.0, which corresponds to a mass of approximately 18 to 229% by weight of the polymer. emphasize that it is advantageous to use solvents with a high specific gravity, e.g. H2SO4 -1.83 g / ml, HS03C11.79 g / ml and HSO3F - 1.74 g / ml, because then the polymer volume factor is higher than when using alkylamides, for example phosphoric acid hexamethylamide and acetic acid dimethylamide with a specific weight of 0.9-1.0 g / mol. A high volumetric ratio is also achieved by using a high concentration of polymer in the pre-quench. In the process according to the invention, it is preferable to use the highest possible pre-quench concentration. It has been found that generally speaking, the tensile strength of fibers is the higher the higher the mass concentration during the interval. Masses with a suitably high concentration are constantly at room temperature and must be warmed up before storage. It is preferable to extrude a pre-batch mass with an intrinsic viscosity of at least 2.0, in particular at least 2.8 ± 0.05 at a C concentration of 30 g / ml, since then a fiber with an internal viscosity of at least 2.0 is obtained. A fiber with a certain intrinsic viscosity may be obtained by using a polymer of moderate viscosity and by operating the process in such a way as to avoid polymer decomposition, or by using a polymer with a higher viscosity and carrying out the process with a slightly higher decomposition * Using the process according to the invention and by proper rinsing and drying to avoid decomposition, fibers are obtained which, before being processed further, i.e. as raw fibers, contain a polymer with a viscosity equal to that of the mass to be passed. unexpectedly lasted. It seems that the "acidity" of sulfuric acid decreases in the presence of a high concentration of rigid chain polyamides. This is confirmed by tests carried out in which the PPD-T polymer with an internal viscosity of 4.88 dissolves in 100 ° C. / with sulfuric acid in the amount of 46 g, 21.8 g and * 3.7 g / 100 ml and heated for 3 hours at the temperature of 100 ° C. Polymer * obtained from these heated heating 15 20 25 30 35 40 45 50 55 6082355 9 10 products have specific viscosities of 4.2, 2.8 and 1.9. Proof of the reduced "acidity" of the pre-partition masses is also the fact that the masses made of PPD-T with a concentration of 46 g / 100 ml are practically taken they do not react with metallic aluminum at 70-80 ° C, while masses at a concentration of 25 g / 100 ml react strongly. Sometimes it is advantageous to vent the liquid mass under reduced pressure before the interval. The present invention, which is a polymer-solvent system, has characteristics similar to those of a polymer melt. A typical mass being a solution of 46 g of PPD-T with an intrinsic viscosity of 4 in 100 ml of 100% sulfuric acid has an apparent viscosity of about 900 poise at 105 ° C. This viscosity increases to about 1000 poise on cooling to 80 ° C, and on further cooling it increases rapidly, and at 70 ° C the solution solidifies to form a dull product. At a certain concentration and temperature, the apparent viscosity is the higher the higher the specific viscosity of the mass. The above-mentioned mass in the liquid state is thin, translucent at a temperature below 135 ° C, and above this temperature it becomes almost transparent. Masses containing about 49 g of PPD-T in 100 ml of sulfuric acid are due to their very high High apparent viscosity with the most concentrated masses which can be processed in ordinary mixers and transported by lines and by pre-mixing equipment. By using the known method of lowering the viscosity by heating, an excessive decomposition of the polymer is caused, so in order to be able to use masses of higher concentrations, more efficient mixers with more efficient cooling must be used. The viscosity at these higher concentrations depends on the polymer-solvent system used. In general, the masses can be extruded at any temperature, from the lowest temperature, which is still liquid, to 120 ° C. Since the degree of decomposition depends on time and temperature, a temperature as low as possible should be used, preferably less than 90 ° C, in particular 70-90 ° C. If for some reason a higher temperature must be used, then the apparatus should be designed so that the mass is exposed to this temperature within the shortest possible time. from the masses used in known processes. They are usually constantly at room temperature, they melt when heated, become less sticky and more transparent, until they are completely transparent. They are optically anisotropic, that is, the microscopic regions of a given mass refract the light twice, and a sample of the mass depolarizes the plane of polarized light because the light-transmitting ability of the microscopic surfaces of the mass varies with direction. These characteristics result from the fact that at least part of the mass is in the liquid crystalline or mechomorphic state. These masses show anisotropic properties when they are in a state of relaxation. A well-mixed pre-agglomerate mass of a specific composition and concentration melts and solidifies at a precisely defined temperature. The melting is accompanied by the absorption of heat, which is confirmed by the results of the differential thermal analysis. The melting point of the solidified masses can also be determined by measuring the intensity of polarized light passing through a thin sample and the analyzer rotated 90 ° as the temperature is raised. The melting point is that temperature at which the intensity of the transmitted light rises rapidly. In general, the melting point of the mass is the higher the higher its concentration, e.g. masses containing 32 g, 40 g and 46 g of PPD-T in 100 g of sulfuric acid melt at 40-50 ° C, 63-65 ° C. C and 72-82 ° C. The mass insufficiently mixed and having an uneven concentration melts at a broader temperature limit. If the temperature of the anisotropic melt is increased, then the point is reached where the amount of the anisotropic phase begins to decline. The temperature (Ta) can be determined by measuring the change in the scattering of polarized light passing under small angles, such as T, through a thin layer of mass. This temperature increases as the concentration of the polymer increases, and for masses containing 32 g, 40 g and 46 g of PPD-T in 100 ml of sulfuric acid it is about 80-100 ° C, 82-135 ° C and 110-122 ° C, respectively. However, even above these temperatures, the masses are largely anisotropic and give good results when used in the process of the invention, but the fibers with the highest tensile strength are obtained by using a range of masses with a temperature above the melting point and below. The invention is described using terms applicable to fiber compartment processes, but this description also applies to foil extrusion. Pre-extrusion nozzles and other machine parts made of strong acid resistant materials are used for extrusion. The diameter of the holes and the ratio of the length of the capillary to the diameter of the hole (L: D) in the nozzle are not critical. High strength fibers are obtained with holes having a circular diameter of 0.025-0.25 mm and an L: D ratio of 1.0-8.3. It is also possible to use nozzles that do not have a circular cross-section, but have a different shape, e.g. in the form of narrow slots of 0.02 mm X 0.05 mm, 0.02 mmX25 mm or 0.175 mmX75 mm. The distance between the nozzles is also not decisive and depends on the material from which the device is made and on the desired linear consistency of the fibers produced. The mass extrusion rate, marked with the symbol JV, is the average mass velocity in the nozzle box, calculated with the ratio of the volume of mass flowing through the opening per unit time and per unit of the cross-sectional area of the nozzle opening. This speed is 5.1-350 m / minute or more. The minimum extrusion speed is calculated for a given mass and a given hole, with the extrusion being carried out continuously, ie without interruptions or disturbances. Smaller diameter holes have a minimum speed greater than larger diameter holes. The pull-ahead ratio, abbreviated SSF, is the ratio of the speed of the fiber exiting the coagulation bath to the extrusion speed, and is 1.0-14 or greater. The lowest draw ratio (which can be used for a given mass and a given die depends on the ability to produce a fiber of relatively uniform thickness and the desired physical properties, and the highest draw ratio is limited by the breaking of the fibers during their production). Taking into account, if at a given extrusion speed the tensile factor SSF increases, we obtain fibers with higher tensile strength and higher modules, but with lower elongation and thickness. In the process according to the invention, the front surface of the nozzle should be separated from the coagulating flue by a gaseous layer and a liquid layer that does not cause coagulation such as toluene, heptane etc. The thickness of this layer is 0.1-10 cm or more, preferably about 0.5-2 cm. The use of a thicker layer creates a risk of adhering fibers sticking together. "The arrangement of the pre-sectional wire 60 (Fig. 1) and the type of guide 57 have an effect on the elongation and the fiber module immediately after advance. With a constant extrusion speed and a constant winding speed, a straight wire As a rule, the pre-port gives a greater elongation and a lower modulus than the knot at the lower end. Likewise, the guide roller provides a greater elongation than the guide pin. In the coagulation process according to the invention, different baths can be used, and good results are achieved with both water and water-free systems. The water systems can be pure water or water containing even high amounts of sulfuric acid (70%). ammonium hydroxide or a salt such as calcium chloride, potassium carbonate, or sodium chloride. Use water baths containing water-miscible organic solvents, such as methanol or ethylene glycol. Non-aqueous baths are, for example, 100% methanol or methylene chloride solutions containing 5 to 50% of methanol, N, N'-dimethylformamide or N, N'-dimethylacetamide. Preferably, a bath temperature of from -25 ° C to 28 ° C is used. While a number of coagulants may be used at a temperature of less than 0 ° C to 50 ° C or higher, but in order to obtain fibers with a very high tensile strength it is most preferred to use 12 baths at a temperature below 10 ° C, especially below 5 ° C. C. Since even the smallest amounts of acid in the rod cause decomposition, complete acid removal is very important for the strength of the fibers. Water or aqueous alkaline solutions are used to remove the acid. A convenient method of rinsing is to spray the fibers leaving the coagulation bath with an aqueous alkaline solution, such as saturated NaHCO 3 solution or 0.05 N NaOH solution, to remove the liquid from the surface of the fibers. with a wiping device, e.g. a sponge, followed by a rinse with 75 ° C water to reduce the acid content to about 1% per dry fiber and winding on the coils. These coils can be stored for a short time, up to about 24 hours, in water or in dilute alkali, and then subjected to a final rinse, e.g. at 75 ° C, which reduces the acid or base content below 0.01% downstream. dry fiber. While small amounts of yarn may be rinsed and darkened on the coils, it is preferable to rinse the yarns in thin layers on rollers, belts, etc. using top spray. In a continuous process, the spines can also be rinsed and neutralized continuously at any point between the lead and the winding point. Thoroughly rinsed fibers can be dried on coils with air heated to a temperature of 150 ° C. They are also preferably dried on heated rolls, e.g. to 160 ° C. If the fibers are dried under a stressed state of less than 0.3 g / denier, which is the most advantageous method, then the properties of the fibers are not significantly affected. changes. The use of a tension greater than 0.3 g / denier reduces the elongation and increases the modulus of the fibers compared to the values obtained by drying without tension. The properties of the green yarn can be altered by applying heat treatment. Heating a stretched fiber, preferably in a neutral atmosphere, at a temperature of 150-550 ° C increases the fiber modulus by about 15-100% and reduces the elongation by about 50%. The increase of the module is the greater the higher the fiber tension and the higher the temperature. Typically, a tension of about 2-12 g / denier and a heating time of 1.5-6 seconds at 150 ° C and 0.5-2 g / denier and 1-6 seconds at 550 ° C are used. When heated at a temperature that is not too high, the tensile strength of the fiber does not change significantly, but when heated at a temperature of 450 ° C. or more, it may be reduced. Typically, the fibers are dried prior to being heat-treated, 60 but it is also possible to heat the wet fibers, immediately after rinsing, or the wetted fibers after drying, the heating time being somewhat longer. Some terms and trials used herein are discussed below. 65 The intrinsic viscosity IV is calculated from the equation: 13 ln-fare. IV = c where c is the concentration of the polymer solution (0.5 g of polymer or fiber in 100 ml of solvent) and rc | that is, relative viscosity, is the ratio of the flow time of the polymer solution to that of the solvent flowing through the capillary viscometer at 30 ° C. Unless otherwise stated, sulfuric acid with a concentration of 95-98% is used as the solvent. The properties of the fibers are determined for fibers kept (unless otherwise stated) for at least 16 hours at 21 ° C and 65% relative humidity. , and the properties of the yarn are measured for the yarn kept for at least 16 hours at 24 ° C and 55% relative humidity. Tensile strength (Ten), elongation or elongation at break (E), starting module (Mi) and Toughness, i.e. dynamic load resistance (Tou), is determined by testing single fibers or multi-strand yarns with an Instron system device. Namely, individual fibers are torn with a distance between the device grips of 2.54 cm, the average of 3 tests being taken. The hoses are twisted to give 3 twists of 2.54 cm under a tension of 0.1 g / denier and subjected to tearing at a distance between the handles of 25.4 cm. All samples are stretched at a constant speed, namely 10% elongation per minute for fibers with E <8% and 60% elongation per minute for fibers with E = 8-100%, with an extension to break The thickness of the individual fibers is calculated from the functional resonance frequency, determined by vibrating a 7-9 cm long fiber under tension, changing the vibration frequency (ASTM D1577-66 method, Part 25, year * 1968) . This fiber is then broken. The thickness of the rod is determined by weighing the rod of a certain length, preferably 90 cm, at a tension of 0.1 g / denier. Tensile strength in g / denier, elongation at break in%, starting modulus in g / denier and dyna load resistance The mics in g / denier according to ASTMD2101 Part 25, 1968 are calculated from the plot of the elongation under load and the thickness in the den. In practice, the measured sample thickness in the desert, the test conditions and the sample determinations are fed to the mathematical machine prior to the start of the test. The machine records the graph of the elongation curve as a function of load to fracture and then calculates the properties of the fiber. It should be emphasized that from the same sample the properties of individual fibers differs from the properties of a multifilament strand of the same fiber. Namely, the tensile strength of the fibers is greater than that of yarns, usually 1.2 times, the elongation at break is also higher, and the modules are lower. In the remainder of the description, unless otherwise noted, all properties quoted refer to the fibers. The physical properties of all yarn samples discussed in the examples are measured with a length of 3 twists per 2.54 cm, i.e. the twist factor TM is equal for a string of different thickness and is calculated by the formula: * number of twists square root z io per 2.54 cm of thread thickness in denier TM - 73 It was found that the initial yoke module decreased as the twist factor increased. For example, a 700 denier yarn module with a twist factor of 1.08 about 5% lower than an equivalent 200 denier yarn with a twist factor of 0.58. The tensile strength and elongation at break for the film are measured in a manner described above in relation to the yarn and the films are stored under such conditions as described above. The films are torn with a distance between the holders of 5 cm 25 and when stretched by 100% in 1 minute. The viscosity of the pre-melting masses is measured with a Brookfield viscometer using spindles No. 7 and 10 rpm. fiber orientation, described by Leroy K. Alexander in Chapter 4, p. 264 of "X-Ray Diffraction Methods in Polymer Science", Wiley-Interscience Edition (1969), is measured by Warhus produces the diffraction pattern of wide-angle x-ray filament 35. The camera consists of a 7.6 cm long collimator tube having a lead gap of 0.0635 cm at both ends, keeping the sample at a distance of 5 cm from the film. 4 ° The pressure in the camera is very low during exposure. The radiation is produced using a Philips X-ray lamp, catalog number 12045, with a copper diffraction lamp with a small focus (catalog number 14000320) and with a beta nickel filter. The lamp is powered by a current of 40 KV and an intensity of 16 milliamperes. The handle, fibers with a thickness of 0.051 cm, is filled with the test sample and all fibers are kept 50 in the arc of rays parallel. The diffraction spectrum is recorded on a medical-grade Kodak X-ray X-ray bottle, NS-54T or an analogous one. Blone is illuminated for a time sufficient to obtain an image corresponding to typical conditions, e.g. one in which the measured diffraction site has sufficient a photographic density, e.g. of 0.2-1.0. Typically the illumination time is around 25 minutes, but for highly crystalline and oriented samples it is preferable to use a shorter illumination time. The arc length is measured in degrees at half the maximum intensity (the angle formed by joining the points of 50% intensity) of one of the main equatorial sites, and this angle is considered to be the orientation angle of the sample. When specifying the samples discussed in the examples below, when more than one major arc is present, the sample gap is taken to be one that occurs at a value above 20. Sometimes, especially in the case of poly (p-phenylenchloroterephthalic acid amide), the spectrum is The diffractive heat-treated fibers do not contain major equatorial points. In such a case two points are usually observed, each on one side of the equatorial position, and the orientation angle of such fibers is measured on the corresponding meridional arc (especially reflection, 006), comparing this angle with the orientation angle obtained in the determination of the dye described below. The orientation angle of the fibers produced according to the invention is determined by the X-ray film densitometric method. The azimuthal distribution of the diffraction arc density is determined with the Leeds and Northrup system microphotometer (catalog number 6700-P1), the electronic components of which have been replaced by micro The Keithley System Ammeter 410 Micro and the values measured by this instrument are recorded in the Spcedomax Recorder of the Leeds and Northrup System. and the center of the diffraction spectrum shifts to fall in the center of the base, then both of these points coincide with the instrument's light arc. The base of the film is shifted so that the light gap passes through the site of the most dense diffraction spectrum, possibly shifting so as to maintain a strictly central position. By rotating the film through an angle of at least 360 °, a trace of the azimuthal intensity is recorded on the corresponding paper with the coordinate axes, obtaining a curve that has two main peaks, in which the intensity axis is considered to be the vertical axis and the angular shift is visible on the horizontal axis. A basic straight line was drawn for each peak, tangent to the minimum points on each side of the peak and from the maximum of each peak perpendicular to the base line. Through the midpoint of each line perpendicularly, i.e. through the "half-intensity" point, a horizontal line is drawn which intersects each leg of the corresponding curves, then the distance between the legs along the horizontal line "half intensity" - transforms into a gap expressed in degrees. The horizontal distance equivalent to a displacement of 360 ° is determined by rotating a point 360 ° and directly measuring the horizontal displacement corresponding to this rotation. For this purpose, for example, the two main peaks mentioned above can be used. The distance between the legs so measured transforms into a value expressed in degrees. The calculated mean values of the two arches are considered to be the orientation angle. The accuracy of these measurements is ± 0.7 ° with a probability of 95%. Method for determining the apparent size of the crystallite. X-ray diffraction spectra of the fibers produced according to the invention are different depending on the chemical structure, crystallinity, and the degree of ordering and orientation. s fibers. The apparent crystallite size (ACS) for each of the major diffraction peaks observed is calculated from the data obtained from the X-ray diffraction spectrum, using reflection techniques to record the intensity and intensity with an X-ray diffractometer. X-ray generators are used to record the diffraction spectrum. Philips system, obtuse angle diffractometer and electronic circuit boards. About 1.5 meters of thread are wound around the sample holder 15 so that the axis of the wire is perpendicular to the mechanical axis of the diffractometer. A customizable Philips system holder is used which has approximately 21 notches 0.2 mm wide along the edge, with a thin lead foil affixed to cover the bottom of the square hole so that only the fibers at the top are exposed to X-rays. By using a nickel filter for copper radiation (1.5418 A), a trace of a sustained intensity from 6 ° to 38 ° 20 is recorded, at a scoring speed of the spectrum image of 1 ° 2 0 per minute and a card speed of 0, 11 cm per minute, at a set-up time of 2, using the scattering and receiving slots of 0.5 ° and a scintillation detector 30 with a pulse height analyzer. The symbol 2 0 denotes the angle between the unbending and the deflected arc. The recorder's full scale deflection is adjusted so that the overall deflection curve remains on the scale. This scale is linear, as large as possible, and preferably represents at least 50% of the maximum intensity. If the test sample is crystalline, its diffraction patterns show many peaks. Typically the two major peaks are located within about 17 to 25 °. 2 0, especially 19 to 24 ° 2 0. In some cases one or two 'peaks are only visible as a ray deflection. which, however, makes it possible to determine their location. Sometimes only one major, narrow crystalline peak is observed. The method for determining the apparent size of the crystallite, the method given in L. E. Alexander X-ray Difraction Methods in Polymer Science, 1969, Chapter 7, is described below. If the sample is not crystalline, then the only feature of the diffraction pattern is a single, very wide peak. In this case, the apparent size of the crystallite is taken to be zero. First, a baseline is established by drawing a straight line between the points on the curve 9 ° 55 and 36 2 0. Then from the top center of the selected peak is drawn perpendicular to the baseline and on this line. at right angles are the midpoint between the peak of the peak and the baseline, and 60 horizontal lines are drawn through this midpoint. This line may cross one peak leg, and when the minimum between the two main peaks is low enough then this line crosses both arms. The width of the selected peak at this point 65 is obtained by taking a straight line at distance from one leg to the line. perpendicularly and multiply it by 2, or measure the distance between the two legs also along this straight line. This distance specifies the width of the peak and is measured in radians, using the 2 G scale to convert the centimeters distance to degrees or radians. If B is the observed line width in the radios, then the corrected line width in f and radios is calculated from the formula; /? =] / B2-b2 where b is a constant value, determined by measuring the peak width along a line located approximately at 28 ° 2 0 on a diffractogram of crystalline silicon powder supplied by the manufacturer of the device (Philips Electronic Instruments, Mount Vernon, NY). The constant b is expressed in radians. The instrument data is as follows: image dotting speed 0.125 ° 2 G per minute, set time constant 8 and card speed l "/ minute. The apparent crystallite size on which a specific reflection depends is calculated from the formula: KX where K is assumed to be equal to unity, / denotes the wavelength of the x-rays, (J is the corrected peak width in radians as discussed above, and G is the Bragg angle, equal to half of the 2 G value of the peak obtained from the dyirak-Jogram. The crystallite (PACS) used in the structure of the fibers and films produced by the process of the invention is defined for those fibers that have more than one major crystalline peak. This value is calculated as the apparent crystallite size for the peak corresponding to the smaller (smallest) peak. values of 2 G. Since the measurement is not perfect, as there are stresses and faults in the crystals, the obtained value is called an "poor" quantity. 2A with a probability of 95%. The quantitative determination of the transverse order of the crystallite is carried out using electron diffraction on thin sections of the fiber. These studies show that the fibers produced by the method according to the invention have a unique transverse arrangement of the crystallinity planes, which has been found to contribute to the increased tensile strength of the fibers. A structure in which there is a set of planes whose average position is parallel to the planes containing the fiber axis and the radius is particularly advantageous. The research is carried out in such a way that the main latitudinal reflections are identified, i.e. the most intense reflections obtained in by the usual X-ray diffraction spectrum, the method described above for the determination of the apparent crystallite size. Most of the fibers produced according to the invention have two main reflections corresponding to a distance d of approximately 3.9-4.9 A. Such fibers have a structure known as "class I construction". Some fibers have only one main reflection of the same distance. and such a structure is referred to as the "Class II structure". For the tests, an electron diffraction instrument is used so marked that in the diffraction spectrum it is possible to identify both of the above-mentioned main reflections of certain thin sections of the fiber, because the test concerns only these major reflections. The density of the main reflections in the electron diffraction spectra is measured in a specific way and the value of the transverse crystallite order (LCO) is calculated. The tests are carried out in such a way that the tested fibers or films are heated in a relaxed state or in a state of slight stress at this point. ¬ at 400-500 ° C within about 10 seconds to avoid fiber decomposition. It is preferably heated by passing the filament through a heated metal tube filled with nitrogen, the filament being tensioned just enough not to allow it to come into contact with the tube wall. A properly aligned fiber bundle, about 1 mm in diameter and 5 cm long, is placed in an epoxy resin, cut out a short length and glued to the end of a conical rod that serves as a handle. The samples of the test film are most easily deposited using small BEEM capsules, e.g. manufactured by Ladd Research Industries, Burlington, Vermont. The conical top of the capsule is cut along the diameter and the cut is made with the edge of the film at an angle of 45 ° to the axis of the capsule, the capsule is then filled with epoxy resin and polymerized. Sections 0.1-0.2 microns thick are cut from the deposited fiber or membrane samples, preferably using a diamond knife and a microtome designed for making very thin sections, cutting at a speed 1 mm per second or less. At the time of cutting, the samples should be oriented so that the edge of the knife is perpendicular to the longitudinal axis of the fiber (the direction of extrusion) in the bundle or sheet. Class I fibers and membranes are cut at an angle of 45 ° down the longitudinal axis of the sample, and the fibers and membranes of II The classes are cut so that the axis of the particle chain is substantially perpendicular to the cross-sectional area as determined by a universal-based polarizing microscope. The cut foil is manufactured to include at least one long side (parallel to the cut direction) and one short side (perpendicular to the cut direction) as the original extrusion surfaces. The cross-sections should not have excessive knife marks, spillage and deformation (see D. Kay, Techniaues for Electron Microscopy, 2nd edition, pp. 220, 1965). The electron diffraction measurement is carried out in such a way that it is prepared as described above. the slices are placed in the electron microscope reticle in the normal position. An AE1-EM-6G electron microscope is used, operating at an accelerating voltage of 100 kV, and then the microscope shutters are brought into the correct position. The microscope is set to diffraction and the diffraction focus is rotated one scale counterclockwise, ie from the diffraction focus position, to obtain an enlargement of about 600 times. The test piece is then rotated until the longitudinal axis of the fiber or film, approximately parallel to the direction of the cut and passing through the center of the cross-section, becomes perpendicular to the edge of the microscope's half-plate-shaped aperture. The ¬m, with a diameter of about 1 micron in the plane of the object, is placed along the short axis of the fiber and centered through the center of the cross-section and perpendicular to the longitudinal axis so that the centering point is one or two diameters away. the opening from the edge of the fiber cross-section. This position is hereinafter referred to as the S position. The diffraction spectrum is then focused, the photographic film moves a little closer than half the distance into the column and the spectrum is recorded. It then rotates the diffraction focus again one division counterclockwise and moves the hole into position along the fiber cross-section axis and centers it at a distant point by a length of one. one or two diameters from the edge of the fiber cross-section. This position is hereinafter referred to as position L. The focal spectrum then focuses, moves the photographic film the entire length into the columns, and records the diffraction spectrum. This procedure is repeated for at least three different sections of the fiber. Fif. 2 shows the cross-section of the fiber 2 at 45 °, with the opening 4, the edge 6 of the half-sheet screen before insertion in position S. The longitudinal axis 8 of the cross-section is perpendicular to the edge 6. The short axis 7 is parallel to the edge 6 and 9 denotes a hole in the L position. The sheet cross-sections are oriented as indicated above. The hole is positioned at any point one or two times the hole diameter from the long edge (S position) or from the shorter section edge (L position). After film development, three photographic negatives are obtained, each of which has two electron diffraction spectra and lines marking the edge of the aperture. Figure 3 shows a typical electron diffraction spectrum in the S position of a fiber produced according to the invention from a polyphenylene terephthalic acid polyphamide) . The reference lines 18 are drawn through the center of the spectrum parallel to the edge of the diaphragm. The spectrum has pairs of diffractive arches 10 * 12 and 14, both gaps in each pair are positioned equally radially about the center of the spectrum and each arc has a point of maximum Density, called "maximum", for arcs corresponding to the principal parallel reflections in the spectrum. These density is measured in a lateral direction along an unshown line called the center line passing through the center of the spectrum. The center of the spectrum is obscured through the high-density circular region 16 caused by the incident electron beam. Gaps 10 and 12 are the main reflections for a class I structure, so they have "maxima". 4 shows the L-position diffraction spectrum for the section shown in FIG. 3. In FIG. 4, as well as FIGS. 5 and 6, the dense portion 20 near the center of the spectrum is omitted and only the main reflections are shown. Fig. 5 shows the diffraction electron spectrum at the S position, with gaps 10, 11 and 12 representing the principal and reflections. The cross section of a fiber made of poly (p-phenyleneterephthalic acid amide) by a method known in the art, usually by wet ranging. gives diffraction electron spectra at both S and L and b positions similar to the item shown. in FIG. 4, the qualitative examination of the diffraction spectra for a Class I construction is carried out as described below, with the spectra suitable for this purpose having the following characteristics. A. The spectrum has at least one pair of "maxima" with the centerline "parallel (± 30 °) to the reference line and meets one of the following conditions: 1) it has a second pair of maxima with the centerline parallel (± 30 °) to the reference line (see fig. 4) 25 or 2) has a second pair of maxima with the center line perpendicular (± 30 °) to the reference line (see figs. 3 and 5) or 3) has a diffraction ring, i.e. main gap 30 360 ° without a maximum. 4) Sometimes these types of spectra may have a second pair of maxima with the same radiality as one of the first pair (see Figs. 5 and 6). 39 B. The spectrum has two main diffraction rings. If the conditions A or B are not met, then a diffraction spectrum or other diffraction spectrum must be generated from the new section from the same section but with a slightly shifted hole surface. the midpoints of both pairs of maxima are perpendicular to each other (30 °) in the S position of the spectrum, then the same reflections in the L position should be either (1) on the center lines parallel to each other (30 °), as in Fig. 3 and 4 or (2) on initially perpendicular (30 °) center lines with mutually alternating internal and external reflections. If condition (1) or. (2) is not met, this is evidence that the cross-section has been distorted and a different cross-section must be tested. In the test spectrum in the S position the maxima and / or the main rings in the spectrum set for the sample are marked a or b. 55 the spectrum has maxima on a line perpendicular (up to ± 30 °) to the reference line (see Figs. 3, 5 and 6), then all rings and / or maxima in both S and L positions of the spectra that have the same the radius, measured from the center of the spectrum, such as these maxima, z is denoted by the symbol b, and any other major maximums or rings that may be present are denoted by the symbol a. If there are no lines perpendicular (up to 30 °) to the reference line, maxima and if (1) there are two pairs of masks, which can be divided by lines parallel (up to 30 °) to the reference line (see arrangement in Fig. 4), or (2) if both reflections they have the form of full rings, or (3) if there is a pair of maxima and rings, then the outer pairs of maxima (bard the outer ring is marked with the symbol b, and the internal symbol a. The qualitative study of the diffraction spectra for the construction of the II class is carried out by examining spectra with the following characteristics: A. spectra have both in S and L positions a single ring or B. a pair of makiim with a centerline which, with an accuracy of 25 ° jeat, either (a) parallel or (b) perpendicular to the reference line at the spectral position and in the The pair of maxima has a centerline which, to within 25 °, is perpendicular or parallel to the centerline as in cases (a) and (b) for position S. The optical density measurement is carried out in such a way that the photographic film is The diffraction pattern is examined with a Joyce-Loebra microdensitometer using a 10X objective, 20: 1 arm ratio, wedge range 1, 6d and a 4 mm square slit. Each spectrum of class I structure is scored along the centerline connecting the maxima approximately parallel to the reference line, and if there is no maximum on this surface (eg for a ring), then the image of the spectrum is scored along the center line. The class II structure spectra, having a uniform ring as the main reflection, are scored twice through the sample mark, namely (1) parallel and (2) perpendicular to the reference line. A spectrum of class II structure, having several maxima, is scored along the center line of these maxima and on a line passing through the center of the spectrum image, perpendicular to the center line. 7 is a densitometric curve 2-1 taken along spectrum line 10 in FIG. 4. The peaks 26 and 28, denoted by a and b, correspond to the maximum 10 and 12 in FIG. 4. The most dense level 30 corresponds to the darkened center of the spectrum and in FIG. 7 shows the baselines. The analysis of the graphs obtained with a denitometer consists in determining the ratio of the peak heights proportional to the density in the diffraction spectrum and the peaks being a and b corresponding to the spectrum. Since the peaks can be close to each other and overlap each other, you may need to make an amendment. The method of making such an adjustment and determining the peak height is discussed below. In all cases, a curve 32 leads to the lower part of trace 34 between the middle track 35 and the lower outer part of the track 36 (see FIG. 8). 1. If the plot has two separate peaks, then the outer frame 27 of the inner peak 26 is extended as a straight line 38 running parallel to the substantially straight portion of the upper outer shoulder 29 of the outer peak 28. Inner, the frame of the outer peak 28 is extended as a straight line 40 running parallel to the substantially growing portion of the upper inner limb of the inner peak 26. The peak height is the smaller, measured vertically, distance between the peak and curve 32 or extension of the limb of the other peak. In Fig. 8, the height of peak 26 is defined by the proto-angle 42 and the height of peak 28 is perpendicular 38. 2. The spectra having two peaks, one separated by one deflection, are mapped in a manner analogous to that described above. Such a mapping is shown in Fig. 9. In the spectral photograph, a sheet of mapping paper is placed and a horizontal reference line is plotted, and a portion of the curve containing the deflection 23 of the undeveloped peak u and the deflection frame 31. The sheet of paper is then moved to the reference line remained horizontal and so that the drawing of the arm coincided with the drawing of the arm 27 of the separated peak and the lower arm 33 of deflection. The drawing is transferred via transparent paper to the original drawing to obtain the corrected frame 44. The peak bend height 28 is the maximum, measured perpendicular, distance between the original and the corrected arm of that peak. The height of the peak separated by 2G means the perpendicular distance of the peak from the line 32, ie the background line of the image. 3. Spectra with a single peak have a height equal to the vertically measured distance of the peak from the background line of the image. A. The spectra with two unseparated peaks have the same peak height and the ratio of both peaks is equal to one. Such a case is shown in Fig. 10, corresponding to the half of Figs. towards shown in Fig. 6 *. The calculation is performed as follows. The sum of the densities of the principal diffractions measured in the half of the dotted image out of the center should be at least 0.5 above the density along the line of the background image. Scoring the overall spectrum should result in a substantially symmetrical image with two left and right peak heights (measured above the background image line), which peaks correspond to the most intense peak of the spectrum, neither of which should be greater than by more than 20% of the average values of the left and right peaks. Based on the structural elements that define the 50 heights of the peaks, the parameter A is determined as a measure of the preferred structure of the fibers and films produced according to the invention. For (a: b) class I structure A = ¦, where a: b denotes the ratio of the heights of legs a and b, and S and L denote positions S and L. (H!: H2) S For Class II structures A = ——, where (Hi: Hfc) r 60 H / i and H2 in a single-ring spectrum represent the peak height in the perpendicular direction and in the direction parallel to the reference line. For a diffraction spectrum with one pair of maxima, a is the height measured perpendicular (up to 25 °) to the reference line, and b is 23 82 355 24 I measured perpendicular to the height b, with S and L representing the respective positions. (Ar) is calculated taking as the basis the value of a and in the right half of the densitometry plot at both positions. The second value of A (Ar) is calculated from the values of a and b respectively in the left half of the graph. The apparent crystallite size (LCO) for a fiber, that is, for a given section, is the mean of Ar and Ax for that section. If these values consist of a finite quantity and an infinite quantity, then the average values of the reciprocals are computed. If both values are infinite, then the mean is also infinite. Table 1 shows the average LCO values and the order of sizes for the three tested fibers, with the symbol 1 representing infinite in the table. Table 1 Example I II A (a) (b) (c) II B IV a ai b bl e ei fhgh hl ij • k kl .1 rs V ac, VIII def 1 g 1 hi Average LCO value i 72 26 i 18 i »i 34 114 1.4 11 68 i 152 118 35 i 1.6 i 7 , 2 38 1.8 1.2 44 6.5 72 462 105 37 65 i Order of sizes ii — i 24 — i 9.5—45 i — i 5.5—34 i — ii — i 29—38 72— i 1.2-1.6 • 3—25 62—79 i — i 96 — i 20—306 27—44 i — i 1 0.9-2.8 i — i • 6.6—8.0 20 —I 1.7—1.9 0.6—2.2 15 — and 5.5—8.3 15—132 154 — and 35 — and 15—81 12—110 i — and LCO values for fibers of such of the polyamide itself, prepared by known methods, is 0-4.5, usually around 1.0. The specific weight of the fibers is measured by the method ASTM D 1505-68, part 27, 1970, but using as a solvent heptane tetrachloride at the temperature temperature 25 ° C. The specific weight of the four loosely braided fibers 1–2 cm long is determined and the average value is calculated. Table 2 gives the specific weight in g / cm8 of the fibers described in the examples, the numbers of which are given in column 1 of this table, with the number of the table and the positions in which the characteristic data of the fibers are given in column 2. 2 Number of the example I II A II A II A II B IV IV IV IV IV IV IV IV IV IV IV IV IV IV IV IV IV VVV VIII VIII VIII VIII VIII VIII Number of the table and item crude fiber, without treatment 9a 9b 9c 5a 5 ax 5b 5e 5er 5f 5 fi 5g 5h 5 hi 5i 5j 5k 5 ki 51 5r 5s 6a 6b 6c 9d 9e 9f 9g 9h 9i Specific weight of fiber 1.44 1.45 1.45 1.45 1.42 1.48 1 , 43 1.42 1.40 1.42 1.41 1.42 * 1.43 1.43 1.46 1.43 1.47 1.39 1.36 1.43 1.46 1.40 1, 45 1.46 1.44 1.45 1.45 1.45 1.44 1.45 1.43 Fibers made according to the invention from fully aromatic polyamides preferably have a specific weight of at least 1.38 g / cm2, since then they do not contain excessive amounts of bubbles, which would cause a significant reduction in the tensile strength. Example I. Poly (acid amide) p-phenylenephthalic acid with an internal viscosity of 5.4 is mixed in a beaker with 99.7% by weight sulfuric acid, using 46 g of polymer per 100 ml of acid, ie 20% by weight. The raw dough mixture is transferred to a mixer consisting of 2 open top cylinders, each with a capacity of about 250 ml, connected by a stainless steel tube, which is also connected by a tee with an S-shaped tube, temporarily closed. Each of the cylinders has a filter filler in the lower part of 15 20 25 30 35 40 45 50 55 6082355 3 to 50 mcm. The mixer is equipped with a number of pistons, each of which is fitted closely to the cylinder. Each piston has a hole which is open when initially inserting the piston to expel the air and then it is choked. The mixer is placed in a water bath at a temperature of about 95 ° C. After 1-2 hours, the polymer-solvent mixture is pumped through the piston from one cylinder to the other five times, and when the resultant leaching mass is then in the first cylinder and the connecting tube, the plug closing the tube in the tube is removed. S-shaped and connects this cable to an electrically heated pre-die head with a stainless steel filter (Dynaloy X5 by Dynamics, Inc., Morristown, NJ and a 1.27 cm pre-die, 50 holes each 0.05 mm. The water bath surrounding the mixer and tubing is then replaced. A short tubing between the water drip and the pre-exhalation head (100 ° C) is wrapped with the steam tubing. through a 1 cm thick layer of air vertically into water at 4 ° C, using a pre-compartmental line similar to that shown in Fig. 1 so as to obtain tensile factor SSF equal to 6.9. The resulting fibers, carefully washed and air-dried, have an intrinsic viscosity. IV = = 4.8 and the single fiber thickness is 0.92 denier by 33 cm. A strand of yarn with a total thickness of 183 denier is made and passed through a pipe 3.05 m long, containing nitrogen at 525 ° C, under a tension of 1.4 g / denier at this speed (about 90 m / minute) so that the residence time of the rod in the tube is about 2 seconds. The front is stretched so that its length is 1.005 of its original length. The obtained raw material and after heat treatment has the following properties: raw material after raw treatment. 2G fiber strength: yarn strength: orientation angle apparent crystallite size Ten E Mi Tou Ten E Mi Tou 26 3.7 750 0.50 22.8 2.8 811 0.314 11.2V 40 A 21 2.2 950 0.23 20 , 5 1.7 1103 0.164 9.0 "109 A 10 15 20 25 30 35 40 45 50 60 Example II. A. PPD-T polymer with an intrinsic viscosity of 6.0 is added to 99.7% sulfuric acid in temperature of 40 ° C in an ordinary mixer with a water jacket. The polymer is added over 2 minutes through the top opening of the mixer, so as to obtain a mixture of 46 g of polymer per 100 ml of acid. The mixer is then connected to a pressure source reduced to 685 mm Hg and raises the temperature of the water in the jacket to 85 ° C by slowly starting the paddle stirrer. After about 12 minutes the temperature of the water in the jacket is lowered to 77 ° C, the temperature of the solution being then 79-82 ° C. After about 2 hours of stirring, the solution has an apparent viscosity of 230.0 poise. The obtained pre-mixture is transferred to a glass-lined and heated plate. with a water connector at a temperature of 90 ° C. For about 30 minutes, the solution is agitated under a pressure of about 690 mm Hg to remove any air that may have entered the solution during transfer, and the mass is pumped through lines surrounded by lines of water at 90 ° C to 90 ° C. pre-runner head electrically heated to a temperature of 50 ° C. By means of a dosing pump, water heated to 80 ° C and containing a sieve and nozzles with a diameter of 12.7 mm, with a minimum of 100 holes and a diameter of 0.051 mm, is pumped into the pre-chamber head. The mass is extruded through the nozzles at a speed of approx. , lo 63 m / minute vertically through a 5 mm layer of air into water 9 at 1 ° C, using the pre-split tube shown in Fig. 1 Fiber samples a and b are prepared by using a freely rotating roller under the pre-split tube, which directs the coil to winding, while the sample c is prepared using a ceramic rod. The wires are wound at different speeds on a coil in water at 50 ° C and the coils from the front are stored in a tank of water. The coils are then immersed in 0.1 N NaHCOO solution, and rinsed with water at 70 ° C using the apparatus described in US Pat. Am. No. 2,659,225. The washed strand is wound up and dried on spools at 70 ° C. The properties of the samples, a, b and c, having an intrinsic viscosity of 5.2 after drying, are given in Table 9. This interval has a tensile index of 1.5, 3.4 and 4.4.B. Pre-quenching mass containing 46 g of PPD-T polymer with an internal viscosity of 5.9 in 100 ml of sulfuric acid with a concentration above 998 / t by weight is mixed and extruded through a slit of 0.63 × 8.9 mm at a speed of about 19.5 m / min, through the 3.2 mm thick air layer to a vertical trough with dimensions of 1.6 × 25 mm, containing water at a temperature of 7 ° C, and the resulting film is led under a ceramic rim and wound on coil with a pull factor of about 2.3. The coil is sprinkled with a saturated aqueous solution of NaHCO3, then rinsed with water and dried, obtaining a film of 871 denier thickness, which, when stretched by 100% for 1 minute, with a grip distance of 5 cm, exhibits the following properties: Ten = 18, E -5.7 and Mi = 360. Strength tests are carried out in the conditions described for the fibers. The film has an intrinsic viscosity of at least 5.0.27 82355 28 Example III. PPD-T intrinsic viscosities with an intrinsic viscosity of 5.4 (4.6 for samples f, k, m and n in Table 3) are prepared with various acids and possibly the additives listed v in Table 3. Initially, they are mixed by hand and then steps in the mixer described in Example I over a period of 15 to 120 minutes. The masses are extruded with the apparatus described in Example I, using pre-chamber nozzles with 20 holes, 0.076 mm in diameter and guiding the threads through a 1 cm layer of air into the water at a temperature of 1-3 ° C, and then wound up , rinses the steady water and dries on the coil. * HSO3Cl, HSO3F, a mixture of HSO3 and H2SO4 in a weight ratio of 49:51 and 100% sulfuric acid are used as the solvent, respectively for samples a, b, c, d. Sample e contains a mixture of FSO3H and HF as solvent, while samples f - n have sulfuric acid as solvent with the additives given in Table 3. The winding speed is from 185 m / minute (sample j) to 610 m / minute (sample g). The concentration of the pre-melting mass is from 34 (sample a) to 47 g of polymer per 100 ml of solvent with additive (sample f). The process conditions and the properties of the fibers are given in Table 3. It has been found that if sulfonic acids are used as additives (tests f, g) then a mass of lower viscosity is obtained than with sulfuric acid alone. The mass containing hydrochloric acid (sample e) has a melting point about 50 ° C lower than the mass containing hydrofluoric acid (sample b), and may also be passed at a lower temperature. The sample g has an extremely high modulus for the raw yarn, that is, with no further treatment. Likewise, high values are shown by the fibers obtained from pulp containing trifluoromethane sulfonic acid as additive. The additive content that can be used in the pulp under normal overtaking conditions is limited and, for example, at an additive / solvent ratio of 60:40 (sample f ) you get a paste that cannot be extruded. With a 20:80 additive to solvent ratio and 20% polymer (sample m), the mixture is so viscous that it cannot be extruded, while an additive / solvent ratio of 40:60 (sample j) gives a mass in the form of dry lumps. The properties of the fibers obtained are given in Table 3 using the abbreviations, the meaning of which is explained above in the description. The thickness of the fibers is given in denier / 33 cm. Example IV. The various polymers are prepared by dissolving the amine in the solvent, cooling the solution to a temperature of about 5-10 ° C, then rapidly adding the dicarboxylic acid chloride with stirring and stirring for at least 1 hour. The polymer is extracted from the mixture in the form of lumps or gels by spraying it in water with a Waring Blendor, draining, rinsing and drying, the process being carried out in a manner known in the art for the production of high-molecular polymers. The monomers used are given in Table 4, with the abbreviation PPD being p-phenylenediamine and the abbreviation TCI being terephthaloyl chloride. The conditions of the polymerization process are given in Table 5. If 2 monomers of the same are used, Sample a b c d e f g h and j k. 1 mn Additive to solvent no additive no additive no additive no additive hydrofluoric acid trifluoromethanesulfonic acid 1,1,2,2-tetrafluoroethanesulfonic acid p-chlorobenzenesulfonic acid trifluoroacetic acid dichloroacetic acid 2,2,3,3 -tetrafluoropropanol-1 hexafluoro-isopropyl alcohol 2,2,2-trichloroethanol nitrobenzene Solvent to additive ratio 100/0 100/0 100/0 100/0 80/20 50/50 80/20 ~ 80/20 80 / 20 80/20 80/20 80/20 82/18 | 88/12 Polymer Ta '16 20 20 20 22 20 20 20 17 20 17 17 17 18 table 3 Shear temperature - wc 50 60 60 86 37 80 102 114 77 99 80 110 80 80 Tensile factor SST 4.0 3.5 4.1 6.4 1.3 7.7 12.2 5.8 4.7 4.1 4.3 4.4 5.0 | 3.6 '' Fiber properties 1 Ten 21 21 26 27 17 22 21 19 25 17 14 18 15 1 15 E 6.8 ¦'4.7 5.6 4.3 3.7 3.9 2.8 2, 9 5.2 3.9 4.7 4.4 3.7 | 4.3 Mi 430 600 440 640 460 630 810 740 470 560 430 520 570 390 thickness 2.3 4.1 2.9 2.3 6.6 1.5 1.3 • 1.1 3.0 3 , 2 2.5 3.4 3.5 3.3 IV 4.5 5.1 5.2 5.0 5.0 4.3 4.7 4.5 4.5 4.0 4.1 5, 0 4.4 4.282355 29 of my type, the ratio in which they are used is indicated. The solvents used are mixtures of 2 solvents, namely hexamethylphosphoric amide (A) and N-methylpyrrolidone (B). The exception is sample a in which only N, N-dimethylacetamide (DMAc) is used and sample j in which equal volumes of B and DMAc are used. The weight ratio of the two solvents is given in Table 5 as the weight ratio of the solvent to the total amount of monomers. Pre-partition masses are prepared using 99.7 to 100% sulfuric acid, or a 1: 1 mixture by weight of sulfuric acid and sulfuryl chloride in the samples j. , 1 and n, with a ratio of 1.15: 1 in sample b. 46 g of polymer are used per 100 ml of acid, ie 20% by weight. In some samples, polymer mixtures obtained by several polymerization processes are used. Pre-cutting masses are extruded through pre-extermination heads at a temperature of 51 ° C to 100 ° C, except for test j, where the temperature is 35 ° C. using the apparatus described in Example I and the nozzles having a diameter of 0.051 or 6.076 mm. It is extruded through a layer of air 0.5-1.9 cm thick into water at a temperature of 0 ° -4 ° C, winding the fibers at a speed of 71 m / minute in the test up to 438 m / minute in the test p. it is thoroughly water and dried on the spools. The tensile coefficients and the properties of the fibers are given in Table 5. The internal viscosity in tests e and e is measured at a concentration of 0.1 ° / o. The above-mentioned method can be overtaken in the form of fibers by the following polymers: copolymer 20/80 given in item q, copolymers 5 / 95 given in items c, d, m and o, as well as the homopolymers of items n and p in Table 4. A processing mass containing 56 g of polymer in 100 ml of sulfuric acid (23% by weight) obtained from chloro-p-phenyleneterephthalic acid liamide) with an intrinsic viscosity of 4.1 will perform well in the above-described manner to obtain fibers with a tensile strength of 17 g / denier. Table 4 Sample a a and bcde 1 ghijk 1 1X1 no Diamine - chloro-p-phenylenediamine acid chloride - TC1 chloro-p-phenylenediamine / PPD - TC1 1,2-bis / p-aminophenyl / -ethane / PPD - TC1 3,3'-dimethylbenzidine / PPp - TC1 m-phenylenediamine / PPD - TC1 PPD-4,4'-dibenzoyl chloride / TCl PPD - fumaryl chloride / TCl PPD - 4,4'-azobenzene dicarbonyl chloride / TC l PPD - chloroterphthaloyl chloride / TCl PPD - isophthaloyl chloride / TCl PPD - chloroterephthaloyl chloride PPD - trans-hexahydrogen terephthaloyl chloride / TCl 4,4'-diaminodulenyl ether / PPD —TC1 PPD - sebacyl chloride / TCl PPD - TCl 2,6-naphthalene dicarboxylic acid 4,4'-diaminodiphenylmethane / PPD— TC1 Poly / chloro-p-phenylene terephthalic acid amide polymer / chloro-p-phenyleneterephthalate amide copolymer and p-phenyleneterephthalic acid amide copolymer 4 , 4'-dubenesylene and p-phenyleneterephthalic acid amide copolymer of 3,3'-Dinnethyl-4,4'-diphenylene and p-phenylene • terephthalic acid amide copolymer of m-phenyleneterephthalate and p-phenyleneterephthalic amide copolymer p-phenylene-4,4'-di-phenylenedicarboxylic and terephthalic copolymer of p-phenylene fumaric acid amide and terephthalic amide copolymer of p-phenylene -4,4-azobenzene dicarboxylic acid and terephthalic amide copolymer of p-phenylene chloroterephthalic acid and chloroterephthalic acid terephthalic amide copolymer of p-phenylene isophthalic acid and Terephthalic poly amide p-phenyleneterephthalic acid amide copolymer of p-phenyleneterephthalic acid amide and terephthalic acid. / p-phenylenaphthalene-dicarboxylic acid amide-2,6 copolymer of 4,4'-methylenediphenylene and p-phenylene terephthalate Polymer symbol Cl PPD - T Cl PPD / PPD - T DDEi / PPD - T DiMePP / PPD - T MPD / PPD - T PPD - BB / T PPD - ZI4 / T PPD - BN2B / T PPD - C1T / T PPD - I / T PPD - C1T PPD - HT / T POP / PPD - T PPD - 10 / T PPD - 2 , 6 N DDM / PPD - T 182 355 31 32 cd Table 4 Prota P qr Diamine - acid chloride 2-methyl-p-phenylene-diamine dihydrochloride. - TC1 PPD - oxalyl chloride / TCl PPD - pyridine-dicarboxylic acid chloride-2.5 Poly / acid amide polymer 2- methyl-p-phenylene-terephthalic amide copolymer of p-phenylene oxalic acid and poly / p-phenylenopyridine-dicarboxylic acid amide poly / p-phenylenepyridine-dicarboxylic acid-amide. - ba a ai befghij hl k ki 1 rs ei fi bi Polymer Cl PPD - T Cl PPD / PPD - T 25/75 DDE / PPD - T 7.5 / 92.5 PPD / BB / T 55/45 PPD- / 14 / T 40/60 PPD — BN2B / T 5/95 PPD — Cl T / T 5/95 PPD — I / T 5/95 PPD — C1T PPD — Cl T / T 50/50. PPD — HT / T 25/75 PPD — HT / T 50/50 POP / PPD — T 5/95 PPD-2.5 Pyr PPD-2.6 N / T 50 / 50.PPD — BB / T 10/90 PPD— / d4 / T 20/80 DDE / PPD — T 10/90 The ratio of solvents A: B 1.0 ^ 1.0 1.0 1.0 9.0 1.0 9 .0 0.96 1.0 1.0 1.0 9.0 1.4 1.0 1.0 0.7 .1 Ratio of solvent to monomers 11.3 3.3 5.6 9.7 15 , 3 4.9 8.5 4.7 7.8 8.0 9.2 9.2 - 5.5 19.8 12.7 10.7 14.7 5.7 1 ab 1 ic a 5 SSF 3.3 3.0 3.1 2.1 4.4 2.1 3.3 3.3 1.7 2.8 6.0 5.5 2.6 4.9 5.3 3.5 3, 9 4.6 IV between 3.9 5.7 3.4 5.3 3.3 3.4 5.5 3.9 3.7 5.0 4.3 3.4 4.3 5.3 6.5 4.3 3.2 Properties of the polymer Ten 18 22 21 21 18 19 23 20 21 21 22 18 24 18 19 26 24 22 E 6.5 6.9 3.8 5.5 5.7 4.6 4 , 2 4.6 4.8 4.5 4.5 4.9 6.2 5.8 5.6 6.4 5.7 3.6 Mi 370 350 730 690 560 500 580 580 640 630 540 490 520 470 580 620 680 730 dpf 3.9 4.3 2.1 3.4 1.6 3.1 4.2 1.5 1.9 1.9 1.4 2.1 2.6 3.5 1, 3 4.1 1.6 1.4 Tou 0.61 0.74 0.43 0.64 0.55 0.45 0.46 0.49 0.54 0.50 0.51 0.47 0.78 0.57 0.56 0.88 0.76 0.41 PACS A 17 0 38 <20 <20 40 43 34 <20 <20 24 31 26 22 0 15 22 37 OA 27.0 23.8 19.6 20.2 18.7 21.8 14.0 16.6 16.4 20.3 15.1 14.8 Example 5 This example relates to polyamides prepared from monomers A-B. The copolymer a given in Table 6 (p-benzamide / p-phenyleneterephthalic acid amide 25/75) is prepared by adding p-aminobenzoyl chloride hydrochloride to a solution of p-phenylenediamine cooled to a temperature of about 6 ° C in a mixture of 10.4 parts by weight of phosphoric acid hexamethylamide and 10 parts by weight of N-methylpyrrolidone. After 5 minutes, the temperature was kept at 6 ° C, and terephthaloyl chloride was rapidly added with stirring, followed by stirring for 5 minutes. The polymer is made as described in Example IV. The monomers are used in a weight ratio of 1: 3: 3. 60 The copolymer b given in Table 6 (p-benzamide / chloro-p-phenyleneterephthalic acid amide 75/25) is prepared by dissolving p-aminobenzoyl chloride hydrochloride and chloro-p-phenylenediamine in N, N -dimethylacetamide, the solution is cooled to about 11 ° C and terephthaloyl chloride is added rapidly while stirring. After standing overnight, the polymer is isolated as described above. The monomers are used in a weight ratio of 3: 1: 1. The homopolymer c given in Table 6, i.e. poly / p-benzamide) is prepared in such a way that to a CN cooled to -10 ° C, N-dimethylacetamide is added with fast stirring, 4- (p-aminobenzamido) -benzoyl chloride hydrochloride, maintaining the solvent to monomer weight ratio of 6.5: 1. After stirring for 2 3/4 hours, the mixture is neutralized with lithium carbonate and stirred for 11/2 hours, and then the polymer is isolated as described above. The internal viscosity of these polymers is from 4.0 (sample b ) to 5.9 (sample a). The precomponent masses are prepared using 99-100% sulfuric acid, with tests a and b being equal to 33 82355 Table 6 Test a b c S.S.F. 4.7 4.5 5.7 Internal viscosity between 5.4 3.9 3.7 Fiber properties Ten 32 * 23 19 E 5.4 4.8 • 4.0 Mi 800 680 570 dpf 1, 9 3.3 1.0 Tou 0.90 0.41 PACSA 32 14 11 OAA 11.9 15.8 approx. 46 g of polymer are taken per 100 ml of solvent (20% by weight), and in the test c. 40 g of polymer are used for 100 ml of solvent (18% by weight). The masses are extruded at a temperature of 37 ° C (test b) to 68 ° C (test c) using the apparatus and method described in example I. Pre-chamber nozzles have a hole diameter of 0.051 or 0.076 mm, the thickness of the air layer is 0.5-1 2 cm, water temperature 1-3 ° C and the fibers are spun at 184 m / minute (test b) to 325 µm / minute (test c). The fibers are rinsed thoroughly and dried on the spools. The properties of the fibers obtained are given in Table 6. Example VI. This example describes some changes to the overtaking process. ' Pre-concentration masses containing 99.7-100% of PPD-T in sulfuric acid are prepared and advanced as described in Example 1, with some specific process conditions listed in Table 7. The pre-concentration masses contain 46 g of polymer. ru in 100 ml of solvent (20% by weight) and only the weight in test e contains 38 g of polymer per 100 ml of solvent (17% by weight). The masses break out at a pre-die temperature of 95 ° C, and only the temperature in tests e, and j is 73 ° C, 85 ° C, and 80 ° C, respectively. Pre-chamber nozzles with a hole diameter of 0.051 mm are used, while in tests c, d, j the diameter of the holes is 0.25 mm, 0.20 mm and 0.076 mm, respectively. is 0.5-1.5 cm. Water is used as the coagulating bath liquid, and only in tests f, g, h sulfuric acid with a concentration of 47.5%, 54% and 70% by weight is used and the tubing containing sulfuric acid is directed under a pretension. ceramic for the second bath, containing water at a temperature of 15 ° C. The winding speed is 198 to 440 m / lm. All the fibers are washed carefully and dried on the spools. The tensile strength of the obtained fibers is given in Table 7. The elongation of the fibers at break ranges from 3.5% to 4.8%, the modulus ranges from 420 g / denier (test e) to 850 g) denier (test f). The thickness of the fibers is 1.1-2.7 denier, and only in tests c, d, the thickness is 12.4 and 10.5 denier. The toughness of the fibers is 0.22-0.69 g / denier. If, in the test, the process is changed by immersing the face of the nozzle in water, then the highest possible winding speed is 27 m / min, with a draw-ahead ratio (SSF) of 0.6, resulting in fibers 9, 2 denier / 33 cm, having a tensile strength of 3.7 g / denier Using the same procedure as in test a, but with an SSF of 3, you get fibers with a tensile strength of 23, 22 and 21 g / denier, with the use of pre-separating pipes with a length of 21.6 cm, 10 cm, and 1.27 cm. the same and the thread tension. In test a, the interval conditions were changed, excluding the mass having a temperature of about 90 ° C (internal polymer viscosity 4.6). steam the 1 cm layer of air vertically into the water bath at 4 ° C. The fibers are taken out of the bath and rolled up at 147 m / minute, with an SSF of 3.0. The rinsed and dried fibers have a tensile strength of 17 g / denier. The process is repeated by using a 1 cm thick layer of toluene instead of the air layer, with the front side of the nozzle immersed in toluene. The results of these tests are given in Table 7. 4.7 / 4.2 4.7 / 4.2 4.7 / 4.5 4.7 / 4.5 4.7 / - 5.4 / - 5.4 / - 5.4 / - 6 , 9 / 5.4 2.8 / 2.8 Extrusion temperature ° C about 95 about 95 about 95 about 95 73 about 95 about 98 about 95 about 85 about 80 Table 7 Coagulation bath temperature ° C 5.5 2 4 4 23 3 5 4 3 3 Tensile factor 3.9 3.9 12.1 10.5 6.0 4.1 3.1 4.4 5.8 4.0 Tensile strength 25 22 17 17 16 23 21 20 30 16 Changed process parameter Bath temperature Bath temperature Large fiber thickness Large fiber thickness Polymer concentration Acid bath Acid bath Acid bath Internal viscosity Specific viscosity 82355 35 Example VII. This example discusses the effect of the extrusion temperature of the sheath on the course of the process. A mass containing 100 ml of sulfuric acid at a concentration of 99% by weight 46 g of a polymer obtained from PPD-To with an intrinsic viscosity of 5.2 is extruded in a manner analogous to that described in Example II, using a pre-chamber nozzle having 100 holes. 0.05 mm in diameter. The mass is extruded through a layer of air approximately 4.8 mm thick into the water at a temperature. 5 ° C. The filament is wound at a speed of about 153 meters / minute with a tensile ratio of about 4.7-5.5. The pre-mass in the reactor is kept at a temperature of about 85 ° C, and the temperature of the conduit to the head, the temperature of the head and the pre-pre-mass nozzle are regulated so that the temperature of the extruded mass has the values given in Table 8. This table gives the properties of the fibers obtained in each trial. 36 Extrusion temperature, internal viscosity Tensile strength Elongation at break Modul Denier / 33 cm Table 8 Test number a 85UC 4.8 24 5.0 484 1.3 b 100UC 4.5 22 4.6 458 1.3 c 110— —115 "C 3.9 19 4.5 414 1.3 d 115— —A20UC 3.2 11 3.9 303 1.5 Example VIII. Poly / p-phenyleneterephthalic acid amide fiber / is prepared as described in Example IIA, using the changes discussed below. The properties of the fibers are given in Table 9 for tests d - i. The extrusion temperature is 85 ° C, and only in the test it is 95 ° C. Water with a temperature of 1 is used as the coagulation bath. -4 ° C, and in the test and water at a temperature of 20 ° C. In tests d, c, f, h, a guide roller is used, while in tests g, a ceramic rod is used. In tests o, h are extruded from nozzles having 570 and 285 holes. All the nozzles have holes with a diameter of 0.05 mm, only in test f the diameter of the holes is 0.15 mm and the holes are only 20. The extrusion speed is from 2 1 m / minute (f test) to 58 m / minute (i test). The stretching ratio for extrusion is from 3.5 (test i) to 5.2 (test d). In test g, the mass is prepared by fusing the solid and granulated mass in a heated screw device. before the water drenched winding device, a feed wheel sprayed with a NaHCO 3 solution is used. In these tests, the coils are stored in water, then in a dilute sodium hydroxide solution, and then fed to a pulling device. In these tests, the fibers are dried on fights heated to 120 ° C. In the tests, d, g of the fibers are rinsed with a water solution. formation of NaHCO 3 in the winding and in the bath before the extraction device. In test d, the fiber is dried at 40 ° C and in test g at 75 ° C. The yarns in tests d, g, h have 6, * 4 and 2 strands. The fiber properties in tests d, e, h are determined to be 5.5 and 4 breaks, respectively. The fibers produced as described in this example are particularly suitable for the manufacture of vehicle tire cords. The yoke used for this purpose should have an intrinsic viscosity of at least 4.0, a tensile strength of at least 18 g / denier and an elongation at break of at least 3%, and it is particularly preferred to use an intrinsic viscosity of 4.5 for this purpose. , a tensile strength of 20 g / denier, an elongation at break of 3.5%, and a tensile strength of 0.35. The fibers of such a yarn have a thickness of less than 2.5 denier / 33 cm, preferably less than 2.0 de ¬ stainless / 33 cm. The tensile strength of the yarns, elongation at break and the dynamic strength of the yarns for making cord cords measured at 150 ° C should preferably be at least 70% of the corresponding values measured at 24 ° C. Abcdefghi Test Specific Viscosity 5 , 2 5.2 5.2 5.2 4.7 5.4 4.7 4.8 5.2 PACS A 45 49 49 38 48 39 49 51 47 Table of properties of yarn OA 20.0 13.9 11.5 22.4 16.0 14.6 15.8 17.2 | 15.3 Ten 21.2, 22.8 24.8 21.9 23.2 21.5 21.1 25.0 | 18.2 E 3.9 3.2 2.8 4.1 3.6 3.5 3.4 4.1 3.0 Mi 547 727 948 459 575 629 556 529 586 Tou 0.39 0.35 0, 34 0.41 0.39 0.35 0.34 0.52 0.26 d Single fiber thickness 3.7 1.9 1.4 1.3 1.2 12.5 2.0 1.2 1 , 8 Thicker 415 190 135 774 710 253 780 702 176 Fiber properties Ten 26 27 27 22 24 21 24 28 21 E 5.6 4.8 4.3 4.2 4.5 4.7 4.6 4.8 4.1 Mi 570 680 680 510 520 600 630 580 510 Tou 0.73 0.67 0.62 0.46 0.53 0.50 0.57 0.67 0.43 | 82355 37 PL PL PL PL PL PL

Claims (7)

1. Claims 38 1. A method of producing fibers or films from polyamides by extruding the pre-quench mass through an opening into a layer of inert fluid that does not cause coagulation and then into a coagulation bath, using a polyamide-containing pre-quench mass consisting of from the repeating group of formula I, in which R is a bivalent radical, and n is the number 0 or o 1, of the group of formula II, in which R 'is a divalent radical and the group of formula III, in which R "is a bivalent radical, where R, R 'and R "are the same or different, and if the polyamide contains groups 1 and 2, then they are in equimolar amounts, and at least 95% by mole of the total number of R radicals, R 'and R "are single rigid radicals with advanced bonds or a series of such rigid radicals linked directly to each other by means of extended bonds, whereby ring-shaped rigid radicals may be allowed to flow. containing azo or azoxyl groups, and the solvent contains sulfuric acid with a concentration of at least 98%, sulfuryl chloride, sulfuryl fluoride or mixtures thereof, characterized in that a polyamide solution in a solvent with a concentration of At least 30 g per 100 ml of solvent and a polyamide with an intrinsic viscosity of at least 2.0 but not less than 2.8-0.05 at a concentration of 30 g / 100 ml of solvent. 2. The method according to p. A pre-limestone mass containing a polyamide consisting of the repeating group of the formulas 1, 2 and 3, in which R, R 'and R "have the meaning given in claim 1, and n in the formula are extruded. 1 is the number 1, whereby if in the polyamide there are simultaneous groups of formulas 1 and 2, they are in equimolar amounts and at least 95% mol of the radicals R, R 'and R ", which are the same or Various are aromatic radicals with advanced bonds, the polyamide being dissolved in a solvent essentially containing only sulfuric acid at a concentration of at least 98%, sulfuryl chloride, sulfuryl fluoride or mixtures thereof, and the concentration of the polyamide in in the solvent is at least 30 g per 100 ml of solvent, and the specific viscosity of the polyamide is at least 2.8. 3. The method according to p. A process according to claim 2, characterized in that • the mass is extruded at a temperature lower than 120 ° C. 4. The method according to p. A process according to claim 1, characterized in that a mass is extruded which is a solid product at a temperature of 25 ° C, and the extrusion process is carried out at a temperature of 40-120 ° C. 5. The method according to p. The method of claim 1, characterized in that the mass has a concentration of 40-56 g of polyamide per 100 ml of solvent. 6. The method according to p. The process of claim 2, wherein the polyamide is poly (p-phenyleterephthalic acid amide) in a concentration of 40-56 g per 100 ml of solvent. 7. The method according to p. The process of claim 1, wherein the mass is extruded at a temperature of 70-90 ° C. R9.1 Fiq.70 o 1 (CRC Formula 7 34 \ 42 - ^ - 32- "Fig. 8 r26 n 1J / \ 28 r \ ft / \ Yl-31 ^ 1 V3" - ^^ J 0 1 1 -c H 1 -R "-N Formula 3 (o) - Formula 5 HHI, I NRN- Formula 2 Formula 4 Formula 6 O Formula 7 -N Formula 8 Fig. 10 O Formula Bag K) HH ccc = c Formula UH oVi IH Pattern 12 Printing works UP PRL Mintage 120 + U Price PLN 10 PL PL PL PL PL PL