RU2017866C1 - Molded article - Google Patents

Abstract

FIELD: molded articles. SUBSTANCE: molded articles based on aromatic copolymides of the p-structure have the structural formula I:

wherein m is 0.2-0.8 and m+n is 1.0 or the structural formula II:

wherein m is 0.1-0.7, 1 is 0.05- 0.65 and m+n+1 is 1.0, wherein Ar₁, Ar₂, Ar₃ and Ar₄ are divalent aromatic radicals in the para-position; having the formula:

wherein R is a CP atom or H;

wherein R₁ is alkyl, C₄ alkoxy, a halogen atom or H; Ar₃ is a heterocyclic radical of the formula:

wherein Y is an O, N, S atom or NH; Ar₄ is a radical of the formula:

and has a disorientation angle of at least 2°; a linear density of at least 25.2 tex a breaking strength of at least 170 gs/tex, an initial elasticity modulus of at least 9100 kgf/mm²; an elongation of 2.0-3.8; a linear expansion coefficient of 4.0·10⁷ mm/deg at 20-50 C and (7.0-8.0)·10^-6 at 50-100 C; an oxygen index of 35-45; and a breaking stress of at least 320 kg/mm². EFFECT: improved properties of molded articles. 3 tbl

Description

 The invention relates to the technology of molded articles, for example fibers, filaments, films, foils made of aromatic copolyamides of n-structure, with high mechanical properties and used for reinforcing plastics, in rubber products, as tire cord and technical materials for filtration and insulation.

 One of the important properties leading to the widespread use of aromatic polyamides in various branches of technology is their resistance to high temperatures, chemicals of various nature, as well as limited combustibility.

 Filaments and films from such materials have very good mechanical properties, for example, high strength and an initial module, and are used for reinforcing plastics, in rubber technology, etc.

Aromatic polyamides are prepared by reacting aromatic diamines with aromatic dicarboxylic acid chlorides in aprotic organic solvents of the amide type such as N, N-dimethylacetamide (DMAA), N-methylpyrrolidone (N-MP) and others with CaCl ₂ and LiCl additives. Filaments with high strength and a high initial modulus are obtained from polyamides in which divalent arylene residues are joined in the para position, thereby forming rigid rod-shaped macromolecules.

Known aromatic polyamide fibers obtained from polyparaphenylene terephthalamide (PFTA), which have a filament strength of 22 g / d and an initial module of 900 g / d. They are obtained by dry-wet method from PFTA solutions in conc. H ₂ SO ₄ [1].

NH

NH - CO

CO

с прочностью 126 гс/текс и модулем упругости 170 г/д. Волокно обладает низкими физико-механическими свойствами [2].Known fibers obtained from an anisotropic polymer solution of the formula

NH

NH - CO

CO

with a strength of 126 gf / tex and an elastic modulus of 170 g / d. The fiber has low physical and mechanical properties [2].

C

NH-CO

CO

NH

NH-CO

CO

Прочность волокон, полученных формованием из анизотропных сернокислотных растворов таких полимеров, достигает 270 гc/текс и начальный модуль 9175 кгс/мм² [2]. Известные волокна обладают низким начальным модулем.Known fiber from copolyamide containing amide and heterocyclic units of the formula

C

NH-CO

CO

NH

NH-CO

CO

The strength of the fibers obtained by molding from anisotropic sulfuric acid solutions of such polymers reaches 270 gf / tex and an initial modulus of 9175 kgf / mm ² [2]. Known fibers have a low initial modulus.

 All of these fibers are obtained from anisotropic solutions in concentrated sulfuric acid. The polymer is first obtained by low-temperature polycondensation in an amide solvent, precipitated, washed, dried, and then the polymer is re-dissolved in acid. Therefore, the process of obtaining such fibers is not economical.

NH - -NH-Ar^I -NH- -NH

R

NH - где Ar и Ar^I - двухвалентные ароматические остатки с валентными связями в пара-положении, R:CH₃-, CH₃O-, Cl;
R ^I - метиловый остаток или группировка -O-Ar-O [4]. Приведенные сополиамиды могут перерабатываться из растворов в апротонном растворителе в формованные изделия, например, волокна и нити с прочностью до 201 cН/текс и начальным модулем до 7900 cН/текс 11455 кгс/мм².The closest technical solution is a solution in which copolyamide-based fibers having repeating structural units —OC — Ar — CO— —NH are disclosed

NH - -NH-Ar ^I -NH- -NH

R

NH - where Ar and Ar ^I are divalent aromatic residues with valence bonds in the para position, R: CH ₃ -, CH ₃ O-, Cl;
R ^I is the methyl residue or the group —O — Ar — O [4]. These copolyamides can be processed from solutions in an aprotic solvent into molded products, for example, fibers and threads with a strength of up to 201 cN / tex and an initial modulus of up to 7900 cN / tex 11455 kgf / mm ² .

 However, these properties in some cases are not high enough.

CO-Ar₁-CO-NH-Ar₂-NH

CO-Ar₁-CO-NH-Ar₃-NH

]_q
при m = 0,2-0,8
и m+n = 1.0 или II

-NH)_m(CO-Ar₁-CO-NH-Ar₃-NH

CO-Ar₁-
при m = 0,1-0,7; l = 0,05-0,65 и m+n+l = =1,0 где Ar₁, Ar₂, Ar₃, Ar₄ - двухвалентные ароматические остатки в пара-положении, причем Ar₁ является остатком дикарбоновой кислоты формулы
Cl-CO

CO-Cl (A) где R - атом Cl или Н; Ar₂ - является остатком диамина формулы
H₂N

NH₂ (B) где R^I - алкил-радикал, алкокси-радикал или атом галоида;
Аr₃ - является гетероциклическим радикалом формулы
_

(C) где y - атом 0,S,NH
Ar₄ - является остатком диамина формулы H₂N

NH₂ (D c характеристической вязкостью 5,9-10,9 дл/г, линейной плотностью 25,4-27,8 текс. углом разориентации 2-4^o, прочностью на разрыв 170-250 гс/текс, удлинением 2,2-3,8% начальным модулем упругости 9100-16000 кгс/мм², влагопоглощением 1,5-4,2%, кислородным индексом 35-45 и коэффициентом линейного термического расширения в интервале температур 20-50^oC 4,0 ˙10^-7, в интервале температур 50-100^oC (7,1-8,0) ˙10^-6.The problem to which the claimed invention is directed is to obtain molded products with enhanced physical and mechanical properties. The necessary technical result is achieved due to the fact that molded products based on aromatic copolyamides of p-structure, according to the proposal, are characterized by structural formula I

CO-Ar ₁ -CO-NH-Ar ₂ -NH

CO-Ar ₁ -CO-NH-Ar ₃ -NH

] _q
with m = 0.2-0.8
and m + n = 1.0 or II

-NH) _m (CO-Ar ₁ -CO-NH-Ar ₃ -NH

CO-Ar ₁ -
with m = 0.1-0.7; l = 0.05-0.65 and m + n + l = = 1.0 where Ar ₁ , Ar ₂ , Ar ₃ , Ar ₄ are divalent aromatic residues in the para position, and Ar ₁ is the residue of a dicarboxylic acid of the formula
Cl-co

CO-Cl (A) where R is a Cl or H atom; Ar ₂ - is a diamine residue of the formula
H ₂ N

NH ₂ (B) where R ^I is an alkyl radical, an alkoxy radical or a halogen atom;
Ar ₃ - is a heterocyclic radical of the formula
_

(C) where y is atom 0, S, NH
Ar ₄ - is a diamine residue of the formula H ₂ N

NH ₂ (D with characteristic viscosity 5.9-10.9 dl / g, linear density 25.4-27.8 tex. Misorientation angle 2-4 ^o , tensile strength 170-250 gf / tex, elongation 2.2 -3.8% with an initial modulus of elasticity of 9100-16000 kgf / mm ² , moisture absorption of 1.5-4.2%, an oxygen index of 35-45 and a coefficient of linear thermal expansion in the temperature range 20-50 ^o C 4.0 ˙10 ^{- 7} , in the temperature range 50-100 ^o C (7.1-8.0) ˙ 10 ^-6 .

 Molded products are obtained from the copolyamide of the required structure, obtained using a mixture of two diamines (structure I) or a mixture of three diamines (structure 11), interacting with aromatic dicarboxylic acid dichloride (DCA).

Moreover, the composition of the mixture of diamines B and C as a percentage of the total number of diamines used for the synthesis of copolyamide of structural formula I can be selected in the range of 20-80 mol% of each diamine. Moreover, B + C = 100 mol.%. The composition of the mixture of three diamines B, C and D in molar percent of the total number of diamines used for the synthesis of copolyamide of structural formula II can be determined graphically in the triangular coordinate system shown in the drawing. Moreover, the molar fraction of each diamine component lies inside the region bounded by the vertices of the polygon with the following coordinates: point P corresponds to 15 mol.% B, 80 mol. S, 5 mol. % D, point Q corresponds to 5 mol.% B, 80 mol.% C, 15 mol.% D, point R corresponds to 5 mol. B, 25 mol.% C, 70 mol.% D, point S corresponds to 25 mol.% B, 5 mol.% C, 70 mol.% D,
point T corresponds to 75 mol.% B, 5 mol.% C, 20 mol.% D, point U corresponds to 75 mol.% B, 20 mol.% C, 5 mol.% D.

A particularly preferred region is the region bounded by the vertices of the polygon with the following coordinates: point P corresponds to 15 mol.% B, 80 mol.% C, 5 mol.% D, point Q ^I corresponds to 10 mol.% B, 80 mol.% C, 10 mol% D, point R ^I corresponds to 10 mol% B, 40 mol% C, 50 mol% D, point S ^I corresponds to 25 mol% B, 20 mol% C, 55 mol% D, point U corresponds to 75 mol.% B, 20 mol.% C, 5 mol.% D.

 This area is also shown in the drawing.

при c_→ o
В качестве растворителя для измерения удельной вязкости полимера и последующего разбавления растворов используют ДМАА с добавкой 3% хлорида лития.The characteristic viscosity of the resulting copolyamides is 5.9-19.9 dl / g and is determined by a known method as a cut-off on the ordinate of the direct dependence of the reduced viscosity on concentration:
[η] = l

as c_ → o
As a solvent for measuring the specific viscosity of the polymer and subsequent dilution of the solutions, DMAA with the addition of 3% lithium chloride is used.

The polycondensation of a mixture of diamines with aromatic dicarboxylic acid dichloride is carried out in an aprotic polar solvent of the amide type, for example N, N DMAA or N-MP, with the addition of calcium or lithium chlorides to increase the solubility. The polycondensation temperature is 0 ^o C - 25 ^o C. The polycondensation reaction is carried out so that at the end of its polycondensate contains from 4.0 to 5.7% of the polymer. The chemical structure is confirmed by elemental analysis and IR. The data are given in table 1.

 The polycondensation can be stopped by a known technique, for example, by the addition of a monofunctional compound such as benzoyl chloride, acetyl chloride and the like.

 According to the invention, in order to prepare a polycondensation solution with a viscosity required for further processing, the polycondensation reaction can be stopped by non-equimolar loading of dicarboxylic acid dichloride with respect to the mixture of diamines. When the molar ratio of the mixture of diamines and dichloride is equal to 1: (0.97-0.99), a polycondensation solution is formed with the required viscosity in the range of 280-980 P. The characteristic viscosity of the resulting copolyamides varies from 5.9 to 10.9 dl / g

According to the invention, at the end of the polycondensation reaction, there is no need to neutralize the hydrogen chloride bound by the solvent, which greatly simplifies the process of obtaining and processing the polycondensation solution directly into molded products, for example filaments, fibers and films. In this case, the processing temperature of the polycondensation solution does not exceed 20-25 ^o C.

 For the manufacture of molded products, the polycondensation solution of copolyamides described above must be filtered, degassed, and subsequently processed in a known manner into fibers, filaments, films and other products. Fibers, threads can be obtained both by wet and dry-wet methods. As a precipitation bath, an aqueous solution of an amide solvent is used, which is used for the synthesis of copolyamide. You can also use an aqueous solution of salt, for example a solution of calcium chloride or lithium.

Freshly formed fibers are subjected to plasticization drawing up to 120%, passed through a washing bath, through drying rollers at 120-140 ^o C, heat treated at 320-350 ^o C and additionally stretched at 360-420 ^o C by 1-3%.

To obtain films, the polycondensation solution must first be diluted to 1.5-2.5% with an amide solvent, filtered and degassed. Using a scraper, the solution is cast into a film, foil, which is subjected to coagulation in water. The film is then washed with water and dried at 85 ^° C. in vacuo.

 PRI me R 1. Aromatic copolyamide from 100 mol.% Terephthaloyl chloride, 40 mol. 2-chloro-paraphenylenediamine and 60 mol% of 5 (6) -amino-2- (p-aminophenyl) benzimidazole.

3.03 g (0.0212 mol) of 2-chloro-p-phenylenediamine, 7.15 g (0.0319 M) 5 (6) amino-2 (p-aminophenyl) benzimidazole and 10.8 g of lithium chloride are dissolved under nitrogen in 375 ml of anhydrous DMAA. After the diamines are dissolved, the solution is cooled to 8 ^° C and 10.62 g (0.0523 M) of terephthaloyl chloride are added with constant stirring over a period of 50 minutes. The viscosity of the solution then gradually increases and amounts to 520 P. at the end of mixing. The viscous copolyamide solution is additionally stirred for 1.5 hours at 22-25 ^° C. The solution contains 4.5% copolyamide, 2.8% LiCl, 1.0% bound hydrogen chloride (HCl). The dissolved copolyamide has [η] = 7.9 dl / g.

The copolyamide solution is filtered off, degassed and the fibers are formed from it by the wet method. The molding is carried out through a die with 60 holes with a diameter of 0.1 m each into a horizontal coagulation bath consisting of a 55% solution of DMAA in water, at a temperature of 20 ^o C at a speed of 13 m / min. with a negative spinneret hood. The resulting fibers were passed through a washing bath, drying rollers at 123 ^° C and then heat treated at 320 ^° C for 30 minutes. After additional thermal elongation in air at 370 ^o C at a speed of 35 m / min, a fiber of linear density 25.4 tex has the following indicators:
P / U / M / σ = 230 / 3.8 / 13500/470 and a misorientation angle of 6 ^o , where P is the relative breaking load of the multifilament yarn, gs / tex, Y is the fiber elongation at break,%, M is dynamic (initial ) the elastic modulus of the fiber, kg / mm ² , σ is the breaking stress in microplastics, kg / mm ² . The coefficient of linear thermal expansion at 50-60 ^o C = 7.2 · 10 ^-6 mm / deg, moisture absorption 2.2%, oxygen index = 40. The properties of the obtained copolyamide are given in table 2, the properties of the obtained filament in table 3 .

 PRI me R 2. Aromatic copolyamide from 100 mol.% Terephthaloyl chloride, 60 mol. % 2-chloro-p-phenylenediamine and 40 mol.% 5 amino-2- (p-aminophenyl / benzoxazole.

4.95 g (0.0347 M) of 2-chloro-p-phenylenediamine, 5.23 g (0.0231 M) of 5 amino-2-p-aminophenyl / benzoxazole and 12.0 g of lithium chloride are dissolved in 369 nitrogen in ml N-MP. After the diamines are dissolved, the solution is cooled to 10 ^° C. and 11.6 g (0.0572 M) of terephthaloyl chloride are added with constant stirring, i.e. 99% of the equimolar amount to the mixture of diamines. The viscosity gradually increases and amounts to 480P at the end of mixing. A viscous polymer solution is further stirred for 2.5 hours at 20-24 ^° C. The composition of the solution and the characteristics of the copolyamide are given in Table 2. The copolyamide solution was filtered, degassed, and formed by the wet method, as in Example 1. After washing, the obtained fibers were passed through drying rollers at 120 ^° C and heat treated at 340 ^° C for 40 minutes. Then the yarn is additionally subjected to thermal extraction in air at 375 ^o C at a speed of 35 m / min. The properties are given in table.3.

 PRI me R 3 (control). Aromatic copolyamide is obtained analogously to example 2, but add 100% of the equimolar amount to the mixture of diamines terephthalyl chloride. And the viscosity of the solution increases rapidly and after 15 minutes the reaction mixture acquires a gel-like state. The solution is very heterogeneous and cannot be formed.

 PRI me R 4. Aromatic copolyamide from 100 mol.% Terephthaloyl chloride, 80 mol. % 2-chloro-p-phenylenediamine and 20 mol.% 5 (6) -amino-2 (p-aminophenyl) benzimidazole.

6.22 g (0.0436 M) of 2-chloro-p-phenylenediamine, 2.44 g (0.0108 M) of 5 (6) amino-2- (p-aminophenyl) benzimidazole and 11.4 g of lithium chloride dissolved in a stream of nitrogen in 380 ml of DMAA. After the diamines are dissolved, the solution is cooled to 10 ^° C. and 10.8 g (0.0532 M) of terephthalyl chloride are added with constant stirring over a period of 60 minutes. The viscosity of the solution then gradually increases and amounts to 650 P. at the end of the stirring. The viscous copolyamide solution is further stirred for 2 hours at 20-24 ^° C. The characteristics of the solution and copolyamide are given in Table 1.

The copolyamide solution is filtered, degassed, and filaments are formed from it according to the dry-wet method through an air gap of 10 mm into a precipitation bath containing a 20% solution of DMAA in water. The temperature of the precipitation bath is 20 ^o C. Die - 6 ^o / 0,1. Molding is carried out at a speed of 21 m / min with a negative spinneret hood and plasticizing hood up to 70%. The resulting fibers are passed through a washing bath, drying rollers at 120 ^o C, heat treated at 345 ^o C. After additional thermal stretching in air at 360 ^o C at a speed of 30 m / min yarn with a linear density of 25.5 tex. The properties are given in table.3.

 PRI me R 5. Aromatic copolyamide from 100 mol.% Terephthaloyl chloride, 20 mol. % 2-chloro-p-phenylenediamine, 80 mol.% 5-amino-2 / p-aminophenyl-benzothiazole.

The monomers, the amount of which is indicated in Table 2, are dissolved in 456 ml of N-MP. After the diamines were dissolved, the solution was cooled to 0 ^° C. and terephthaloyl chloride was added with constant stirring over 65 minutes in an amount of 13.3 g (0.0669 M). The viscosity of the solution increases and amounts to 950 P. at the end of the dosage. The viscous copolyamide solution is further stirred for 2 hours at 21-24 ^° C. The characteristics of the solution and the resulting copolyamide are shown in Table 2.

Fiber is formed from the resulting solution as in Example 1. A 15% solution of N-MP in water is used as a precipitation bath. After washing, the obtained fibers are passed through drying rollers at 110 ^° C and heat treated first at 345 ^° C for 30 minutes and then thermally drawn at 380 ^° C at a speed of 35 m / min. The properties are given in table.3.

 PRI me R 6. Aromatic copolyamide from 100 mol.% 2-chloroterephthaloyl chloride 80 mol of p-phenylenediamine and 20 mol.% 5 (6) -m amino-2- / p-aminophenylbenzimidazole.

Monomers, the amount of which is indicated in Table 2, are dissolved in 462 ml of N-MP. After the diamines were dissolved, the solution was cooled to 5 ^° C and 17.16 g (0.0723 M) of 2-chloroterephthaloyl chloride were added with continuous stirring over 65 minutes. After additional stirring for 1 h at 23-25 ^o C, the viscosity of the solution was 280 P. The characteristics of the solution and the resulting copolyamide are given in table.2.

The copolyamide solution is filtered off, degassed, and the filaments are formed from it by the dry-wet method, as in Example 4. In this case, the precipitation bath has a temperature of 21 ^° C and contains a 22% aqueous solution of N-MP. The fibers are heat treated at 320 ^° C. and then further thermally drawn at 370 ^° C. at a speed of 35 m / min. The properties are given in table.3.

 PRI me R 7. Aromatic copolyamide from 100 mol.% Terephthaloyl chloride, 70 mol. % 5 (6) -amino-2 / p-aminophenyl-benzimidazole and 30 mol.% P-phenylenediamine.

The monomers, the amount of which is indicated in Table 2, are dissolved in 464 ml of DMAA. After the diamines were dissolved, the solution was cooled to 8 ^° C and 12.64 g (0.0623 M) of terephthaloyl chloride were added with continuous stirring over 55 minutes. The viscosity of the solution thus gradually increases and after additional stirring at 20-23 ^o C for 1.5 hours is 540 P.

The characteristics of the solution and copolyamide are given in table.2. The yarns are formed from the obtained copolyamide solution as in Example 4. The yarns obtained are dried at 136 ^° C, heat treated at 340 ^° C and further thermally drawn in air at 375 ^° C at a speed of 35 m / min. The properties of the thread are given in table.3.

 PRI me R 8. Aromatic copolyamide from 100 mol.% Terephthaloyl chloride, 40 mol. % 2,5-diaminotoluene and 60 mol.% 5 (6) -amino-2 / p-aminophenyl) benzimidazole.

6.94 g (0.0356 M) of 2,5-diaminotoluene as a hydrochloride, 11.99 g (0.0535 M) of 5 (6) amino-2 / p-aminophenyl) benzimidazole and 26 g of lithium chloride are dissolved in 529 ml of DMAA in nitrogen. After the diamines are dissolved, the solution is cooled to 5 ^° C. and 17.9 g (0.0882 M) of terephthaloyl chloride are added with constant stirring over a period of 50 minutes. After additional stirring at 20-22 ^o C for 2 h, the viscosity of the solution is 650 P. The characteristics of the solution and copolyamide are given in table.2.

The fibers are formed from a copolyamide solution as in Example 1. After washing, the resulting fibers are passed through drying rollers at 135 ^° C and heat treated at 346 ^° C for 25 minutes. Then it is additionally thermally drawn in air at 377 ^o C at a speed of 33 m / min. The properties are given in table.3.

 PRI me R 9. Aromatic copolyamide of 100 mol.% Terephthaloyl chloride, 40 mol.%, 2,5-diaminomethoxybenzene and 60 mol.% 5 (6) amino-2 / p-aminophenyl benzimidazole.

4.42 g (0.0320 M) of 2,5-diaminomethoxybenzene, 10.77 g (0,0481 M) 5 (6) amino-2 / p-aminophenyl) benzimidazole and 17.1 g of calcium chloride are dissolved in nitrogen in 527 ml of N-MP. After the diamines are dissolved, the solution is cooled to 0 ^° C. and 16.05 g (0.0791 M) of terephthaloyl chloride are added with constant stirring over 70 minutes. After additional stirring at 23-25 ^o C for 1.5 h, the viscosity of the solution is 590 P. The characteristics of the solution and copolyamide are given in table.2.

From a solution of copolyamide by dry-wet method, as in example 4, the filament is formed. In this case, the precipitation bath has a temperature of 23 ^o C and contains a 23% aqueous solution of N-MP. Molding is carried out at a speed of 20 m / min with a negative spinneret hood and a positive plasticizing up to 75%. The resulting fibers are passed through a washing bath, drying rollers, with a temperature of 141 ^o C, then heat treated at 345 ^o C for 40 min and additionally stretched at 375 ^o C at a speed of 32 m / min. The properties are given in table.3.

 PRI me R 10. Aromatic copolyamide from 100 mol.% Terephthaloyl chloride, 25 mol. % 2-chloro-p-phenylenediamine, 50 mol. % 5 (6) amino-2 / p-aminophenyl / benzimidazole and 25 mol.% P-phenylenediamine.

2.81 g (0.0197 M) 2-chloro-p-phenylenediamine, 8.84 g (0.0395 M) 5 (6) amino-2- (n-aminophenyl) benzimidazole, 2.12 g (0, 0197 M) p-phenylenediamine and 16.5 g of lithium chloride are dissolved in a stream of nitrogen in 565 ml of DMAA. After the diamines were dissolved, the solution was cooled to 8 ^° C and 15.84 g (0.078 M) of terephthaloyl chloride were added with constant stirring over 90 minutes. After additional stirring at 24 ^o C for 1.2 h, the viscosity of the copolyamide solution is 630 P. The characteristics of the solution and copolyamide are given in table 2.

The copolyamide solution is molded by the wet method, as in Example 1. In this case, the precipitation bath contains a 55% aqueous DMAA solution and has a temperature of 24 ^° C. The molding is carried out at a speed of 14 m / min with a negative die drawing and plasticization drawing up to 90%. The resulting fibers are passed through a washing bath, drying rollers with a temperature of 132 ^° C, heat treated at 340 ^° C for 30 minutes and additionally thermally drawn in air at 380 ^° C at a speed of 45 m / min. The properties of the obtained yarn are given in table.3.

 PRI me R 11. Similar to example 9. Other conditions and properties, see table. 1-4.

 PRI me R 12. Aromatic copolyamide from 100 mol.% Terephthaloyl chloride, 50 mol. % 2-chloro-p-phenylenediamine, 25 mol.% 5-amino-2 / p-aminophenylbenzothiazole and 25 mol.% 2,5-diaminomethoxybenzene.

6.34 g (0.0444 M) 2-chloro-p-phenylenediamine, 5.35 g (0.0222 M) 5-amino-2 (p-aminophenyl) benzthiazole, 3.07 g (0.0222 M) 2,5-diaminomethoxybenzene and 18.0 g of calcium chloride are dissolved in a stream of nitrogen in 554 ml of N-MP. After the diamines are dissolved, the solution is cooled to 10 ^° C and 17.89 g (0.0881 M) of terephthaloyl chloride are added with constant stirring over 1 hour. After additional stirring for 2 hours at 21-23 ^° C, the viscosity of the copolyamide solution is 980 P. The characteristics of the solution and copolyamide are given in table.2.

The copolyamide solution is filtered off, degassed, and the fibers are formed from it in a dry-wet method into a water bath containing 20% N-MP, as in Example 4. After heat treatment at 340 ^° C, they are further subjected to thermal stretching at 375 ^° C at a speed of 35 m / min The properties are given in table.3.

 PRI me R s 13-22. In examples 13-22, aromatic copolyamides are obtained as in example 10 using the monomer components shown in table 4. The properties of the solution and the resulting copolyamide are given in table 2, the conditions for obtaining the yarn and its properties are shown in table 3.

Claims (1)

FORMED PRODUCT made of aromatic copolyamide based on aromatic dicarboxylic acid and a mixture of aromatic diamines, characterized in that as an aromatic copolyamide it contains a compound of the structural formula

CO-Ar ₁ -CO-NH-Ar ₂ -NH

CO-Ar ₁ -CO-NH-Ar ₃ -NH

] _q
with m = 0.2 - 0.8;
m + n = 1,0
or structural formula

-NH) _m (CO-Ar ₁ -CO-NH-Ar ₃ -NH

CO-Ar ₁ -
with m = 0.1 - 0.7;
l = 0.05 - 0.65;
m + n + l = 1.0,
where Ar ₁ , Ar ₂ , Ar ₃ and Ar ₄ are divalent aromatic radicals in the para position, and Ar ₁ has the formula

where R is Cl or H;
Ar

where R ₁ is an alkyl radical, an alkoxy radical with 4 carbon atoms, a halogen or hydrogen;
Ar ₃ is a heterocyclic radical of the formula
_

where Y is O, N, S or NH,
Ar ₄ is a radical of the formula

with a characteristic viscosity of 5.9 - 10.9 dl / g and a misorientation angle of at least 2 ^° , a linear density of at least 25.4 tex, a tensile strength of at least 170 gf / tex, and an initial modulus of elasticity of at least 9100 kgf / mm ² , elongation of 2.0 - 3.8%, coefficient of linear expansion at 20 - 50 ^o С, equal to 4.0 · 10 ^-7 mm / deg, at 50 - 100 ^o С - (7.1 - 8 , 0) · 10 ^-6 , with an oxygen index of 35 - 45 and a breaking stress of at least 320 kg / mm ² .

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