Method of manufacturing thread from aromatic heterocyclic polyamide

FIELD: optionally materials.

SUBSTANCE: invention relates to heat-resistant thread manufacture technology and can be utilized in manufacture of special materials for flak jackets, high-pressure containers, and in airplane construction. Thread is made from aromatic heterocyclic polyamide prepared via low-temperature polycondensation of a mixture composed of 25-70 mol % diamine of formula: , where X represents -NH, -S, -O, -N(CH3), and N(C2H5) and Z represents N or C, and 30-75 mol % of p-phenylenediamine with aromatic dicarboxylic acid chloride used in equimolar proportions in organic solvent and in presence of lithium or calcium chloride. Thus prepared solution is molded into water-dimethylacetamide precipitation bath. Thread is rinsed, dried, thermally treated for 10-30 min at 340-360°C, and then is drawn at 230-270°C at heating time 1-3 sec.

EFFECT: improved performance characteristics of thread.

1 tbl, 7 ex

 

The invention relates to the technology of heat-resistant high-strength threads of heterocyclic aromatic polyamides, obtained by the method of low-temperature polycondensation of aromatic diamines with dichloromethane aromatic dibasic acids in the environment aprotic amide solvent in the presence of lithium chloride or calcium.

High-strength high-modulus filaments obtained from such polyamides are widely used in the manufacture of structural materials in aircraft construction, special materials for filtration of hot liquids and gases, vests, large parts of aircraft, vessels for high pressure components for high-speed centrifuges, ropes for deepwater works, deepwater lifting devices or wrecks and so on

Known aromatic polyamide fibers (filaments) of the heterocyclic aromatic polyamide obtained by low temperature polycondensation-based diamines 5(6)-amino-2-paraaminometribensole, 2-chloro-paraphenylenediamine and terephthaloylchloride. In this way these diamines in the estimated quantities are dissolved under nitrogen in anhydrous dimethylacetamide containing lithium chloride. After dissolution of the diamines, the solution is cooled to 8°and permanent premesis the NII add terephthaloylchloride for 50 minutes. The viscosity of the solution thus gradually increases and is at the end of the mixing 520 P.

A viscous solution copolyamid additionally stirred for 1.5 h at 22-25°C. the Solution contains 4.5% copolyamid 2,8 LiCl, 1,0% associated hydrogen chloride (HCl). The solution copolyamid filtered off, Tegaserod and from it is formed into fibers (filaments) on-wet method. Shaping is done through a die plate with 60 holes with a diameter of 0.1 mm each in a horizontal coagulation bath consisting of a 55%aqueous solution of dimethylacetamide in water at a temperature of 20°With a speed of 13 m/min, with a negative spunbond hood. The obtained fiber (filament) were washed, dried at 123°and then thermoablative at 320°C for 30 minutes. After additional thermometere in air at 370°fiber (thread) had the following characteristics: relative breaking strength multifilament yarn - 230 g/Tex, an initial modulus of elasticity - 13500 kg/mm2, ultimate tensile stress in the micro-plastic - 470 kg/mm2[Pat. No. 2017866, BI, No. 15, 1994).

The disadvantage of this method is that when additional thermal drawing in air at a temperature of 370°and above occurs thermal-oxidative degradation of the polymer, resulting in a noticeable loss of strength and, as a consequence, falls destructive nab agenie filament under tension of microplastic, what limits, and in some cases eliminates the possibility of using the products for special purposes.

Prototype - the way to obtain fibre-forming polyamide low temperature polycondensation of a diamine of the formula:

where X: NH, S, O, N(CH3), N(C2H5); Z: N, S,

and the acid chloride of an aromatic dicarboxylic acid in the medium of organic solvent in the presence of lithium chloride or calcium. This method provides for receiving fiber (filament) of the fibre-forming polyamide (as reflected in the examples of text), forming a solution of the polymer in the water-dimethylacetamide the precipitation bath, orientation extraction, washing, drying fiber (filament) and subsequent heat treatment at temperatures from 340 to 360°C for 10-30 min (A.S. No. 646605, BI No. 3, 2003).

However, this method does not allow to obtain fiber (thread) with high breaking stress in tension in the micro-plastic and the initial module above 8700 kgf/mm2.

Task to be solved by the claimed invention is directed, is the expansion of the functional and operational capabilities threads by increasing its strength characteristics.

Complex operational, in particular, the strength properties of yarns laid in their orientation. This hundred the AI is formed by the anisotropic structure of the thread, which determines the subsequent properties of the polymer material. Maximum hardening effect yarn can be achieved with maximum pulling. The process of pulling a variety of chemical fibers is very varied and in each case reflect the specific characteristics of the polymer.

In the proposed method, the optimal temperature range thermolytic air is 230 to 270°C, at which the maximum strength of the thread and, as a consequence, high rates of destructive stresses in micro-plastic. Required technical result is achieved by reducing thermal oxidative degradation of the threads in the supplementary heat extraction at a temperature below the heat treatment temperature.

This objective is achieved in that a method for producing a yarn from a heterocyclic aromatic polyamide comprising the low-temperature polycondensation mixture 25-70 mol.% the diamine of the formula:

where X: NH, S, O, N(CH3), N(C2H5); Z: N, S,

with 30-75 mol.% p-phenylenediamine in the medium of organic solvent in the presence of lithium chloride or calcium with equimolar amounts of the acid chloride of an aromatic dicarboxylic acid, forming the resulting solution of the polymer in the water-dimethylacetamide precipitation in the nnu, washing, drying and heat treatment of the thread in the 340-360°C for 10-30 min, according to the invention, additional heat extractor thread carried out at a temperature of 230 to 270°C for 1-3 seconds at 1-1 .5%.

The method involves the synthesis of aromatic depolimerizatia based on 5(6)-amino-2-para-aminobenzimidazole, paraphenylenediamine terephthaloylchloride

and is implemented as follows.

In a reactor with a stirrer download anhydrous dimethylacetamide, containing for increased solvent capacity lithium chloride and 5(6)-amino-2-para-aminobenzimidazole, stirred for 30 min, then add paraphenylenediamine and stirred for further 10 min After dissolution of the diamines, the reactor is cooled to 15-20°With, then add 80, 90, or 92% of the equimolar ratio terephthaloylchloride, stirred for 30 min and then the remaining number of terephthaloylchloride gradually while cooling add up to obtain a spinning solution of a polymer with a viscosity of 400 to 450 seconds.

The polycondensation reaction is conducted in such a way that at the end of her polycondensate contains from 3.5 to 5.0% of the polymer content of the hydrochloride of 0.9%.

Polycondensation solution after triple filtration and deaeration is used for wet spinning of filaments through the die plate holes 330 is emetrol 0.1 mm into the precipitation bath, containing 48-55%solution of dimethylacetamide in water at a temperature of 25-30°and pH 4-5 with the receiving rate of 12-15 m/min, spunbond hood is -40 to -60%, and orientation extraction, carried out in the coat precipitation bath, from 95 to 130%.

After flushing solvent, salt and hydrochloride, drying the thread thermoablative.

The heat treatment is performed under vacuum to prevent thermo-oxidative degradation processes and to remove residual solvent, moisture, hydrochloride at a temperature of 340-360°C for 10-30 minutes.

Next, to further enhance the module perform additional heat extraction at a temperature of 230 to 270°C for 1-3 seconds of heating filament and a speed of 20 m/min, while the ultimate tensile stress in the micro-plastic reaches 580-600 kg/mm2that far exceeds the measure of the strength of the threads in the micro-plastic in the above analogs.

At temperatures below 230°With the process of thermometere not stable, there are frequent breaks due to the fact that the process is below the glass transition temperature.

With increasing temperature thermal hood above 270°to decrease the strength of the thread and there has been a sharp drop destructive voltage in micro-plastic.

When the heating time is below 1 second thread does not reach temperature 230°S. P and the heating time more than 3 seconds, the thread loses strength properties.

When thermolytic filament linear density of more than 100 Tex or increasing the rate of production it is necessary to adjust the residence time of the yarn in the heated chamber to reach the desired temperature of the thread.

The method is illustrated by the following examples and data are listed in table 1.

Example 1. In a reactor with a stirrer download 16,0 l of dimethylacetamide with humidity 0,034%, containing 2.8 wt.% chloride lithium 349,6 (70 mol.%) 5(6)-amino-2-para-aminobenzimidazole,

stirred for 30 minutes with the mixer rotation speed of 140 rpm, then add 72 g (30 mol.%) paraphenylenediamine,

stirred for further 10 min After dissolution of the diamines, the reactor is cooled to 15-20°With, then add the first 80% of the equimolar ratio terephthaloylchloride 361 g,

stirred for 30 min and then the remaining 20% of terephthaloylchloride gradually while cooling add up to obtain a spinning solution of a polymer with a viscosity of 400 to 450 seconds.

Polycondensation solution after filtration and deaeration is used for wet forming of threads in water-dimethylacetamide bath containing 48-52% dimethylacetamide and 2% lithium chloride, at a temperature of 20-30°With spunbond hood minus 40-55%, Orien is sure hood from 100 to 130%.

After flushing solvent, salt and hydrochloride, drying the thread thermoablative at a temperature of 350°C for 10 min, then further pulled to 1% at a temperature of 230°lower heat treatment temperature.

Ready thread 100 Tex had a strength of 250 g/Tex, an initial module 14500 kg/mm2, ultimate tensile stress in the micro-plastic 580-600 kgf/mm2. The high strength thread.

Example 2. 349,6 g (70 mol.%) 5(6)amino-2-paraaminometribensole and 72 g (30 mol.%) paraphenylenediamine dissolved in 16 l of dimethylacetamide containing 2.8 wt.% chloride lithium.

After dissolution of the diamines add in the beginning of 90% of the equimolar ratio terephthaloylchloride, stirred for 30 min and gradually add the remaining 10% of terephthaloylchloride. From the obtained spinning solution of the polymer is formed into a thread.

The washed and dried thread thermoablative at a temperature of 360°C for 10 min, additional pull by 1.1% at a temperature of 250°lower heat treatment temperature.

Ready thread 100 Tex had the strength of 270 g/Tex, an initial module 15200 kg/mm2destroying the voltage 560 kgf/mm2. The high strength thread.

Example 3. The production of polymer and forming the thread carried out analogously to example 1.

Heat treatment of the washed and dried yarn is carried out at a temperature of 340°within 20 m is h, additional thermolytic 1% at a temperature of 230°C.

Ready thread 100 Tex had the strength of 265 g/Tex, an initial module 14000 kg/mm2destroying the voltage 570 kgf/mm2. The high strength thread.

Example 4. 330 g (65 mol.%) 5(6)amino-2-paraaminometribensole and 86 g (35 mol.%) paraphenylenediamine dissolved in 16 l of dimethylacetamide containing 3.0 wt.% chloride lithium.

After dissolution of the diamines add at the beginning of 92% of the equimolar ratio terephthaloylchloride, stirred for 30 min and gradually cooled add the remaining 8% of terephthaloylchloride. From the obtained spinning solution of a polymer concentration of 4.35% and a viscosity of 500 sec. is formed into a filament in a precipitation bath containing 52% of dimethylacetamide and 48% water, at a temperature of 23°C. orientational hood when it was 102%.

The washed and dried thread thermoablative at a temperature of 350°C for 30 min on a rigid package, optional pull 1.5% at a temperature of 270°lower heat treatment temperature.

Ready thread 100 Tex had a strength of 250 g/Tex, an initial module 15660 kg/mm2, ultimate tensile stress tensile 540 kgf/mm2. The high strength thread.

Example 5. 368 g (75 mol.%) 5(6)amino-2-paraaminometribensole and 59 g (25 mol.%) paraphenylenediamine dissolved in 16 l of dimethylacetamide with what agnosto being 0.036%, containing 2.8 wt.% chloride lithium.

After dissolution of the diamines add cooling to a temperature of 10-12°gradually 444 g (100 mol.%) terephthaloylchloride, stirred for 30 min Obtained spinning solution with a polymer concentration of 4.2% is formed in a precipitation bath at a temperature of 25°C.

Freshly formed yarn is washed, dried and subjected to heat treatment at a temperature of 350°C for 10 minutes Then pull 1.3% at a temperature of 270°and the heating time of 1 sec.

Ready thread 100 Tex had a strength of 250 g/Tex, an initial module 14500 kg/mm2, ultimate tensile stress in tension in the micro-plastic 520 kgf/mm2.

Example 6. The production of polymer and forming the thread carried out analogously to example 1. In a reactor with a stirrer load 314 g (70 mol.%) 5(6)amino-2-paraaminometribensole versus 66.2 g (30 mol.%) paraphenylenediamine in 16 l of dried dimethylacetamide, containing 2.8 wt.% chloride lithium. In the solution when cooled gradually add 422,9 g(100 mol.%) dichlorohydrin terephthalic acid.

From the obtained spinning solution is formed into a filament in water-dimethylacetamide tub. Next thread should be washed, dried and subjected to heat treatment at 350°C for 30 min, then further termwithout 1% at a temperature of 270°and the heating time 3 sec.

Ready thread 100 tech who had the strength of 260 g/Tex, the initial module 14700 kg/mm2, ultimate tensile stress in tension in the micro-plastic 535 kgf/mm2. The high strength thread.

Example 7. (Comparative). The synthesis of the polymer and forming the thread carried out according to example 1, except that thermolytic carried out at a temperature higher than the temperature of the heat treatment at 400°C.

Ready thread 100 Tex had the strength of 230 g/Tex, an initial modulus of 15,000 kg/mm2, ultimate tensile stress in tension in the micro-plastic 390 kgf/mm2. Thread the prototype in micro-plastic strength is considerably inferior declared threads.

The invention will find application in the manufacture of products in organoplastic and in aircraft.

Table 1.
ExampleThe treatment modeTemperature thermolytic, °
Temperature, °Time, minutes230270390
Ultimate tensile stress in the micro-plastic kgf/mm2
135010594540400
236010568560410
334020570534318
435030560540470
535010550520100
635030560535476
The prototype x38020520400390
X - data prototype tested in a production environment JSC JSC "Khimvolokno"

The method of obtaining the threads of heterocyclic aromatic polyamide comprising the low-temperature polycondensation mixture 25-70 mol.% the diamine of the formula

where X is NH, S, O, N(CH3), N(C2H5); Z: N, S,

with 30-75 mol.% p-phenylenediamine in the medium of organic solvent in the presence of lithium chloride or calcium, with equimolar amounts of the acid chloride of an aromatic dicarboxylic acid, forming the resulting solution of the polymer in the water-dimethylacetamide the precipitation bath, washing, drying and heat treatment of the filaments at a temperature of 340-360°C for 10-30 min, characterized in that the thread is additionally subjected to a heat treatment of the tion of the hood at 230 to 270° C for 1-3 seconds at 1-1 .5%.



 

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