RU2712691C1 - Polymer composition and method of producing a spinning solution based on a polymer composition - Google Patents

Abstract

FIELD: technological processes.

SUBSTANCE: invention relates to polymer compositions used for making fibrous materials. Polymer composition contains a metal-containing phthalocyanine additive which is copper hexadecagalogenophthalocyanine in amount of 14.998–4.999 pts.wt. As a polymer, the composition contains a product of copolycondensation of a mixture of terephthalic, isophthalic, paratoluilic, metatoluilic acid and hydrazine sulphate, and metaazobenzenedicarboxylic acid in amount of 85–95 pts.wt. Additive additionally contains carbon nanoparticles in amount of 0.002–0.001 pts.wt. Invention also relates to a method of producing a spinning solution based on said polymer composition.

EFFECT: ensuring preservation of rate of molding, dynamic viscosity and concentration of spinning solution with simultaneous formation of surface layer from carbon nanoparticles on produced filaments when passing through spinneret for molding of synthetic papers with electrostatic properties.

2 cl, 1 dwg, 1 tbl, 1 ex

Description

The invention relates to polymer compositions used for the manufacture of fibrous materials, as well as to the field of chemical industry, in particular to the production of polyoxadiazole fibrous materials used to produce synthetic papers used as electrostatic materials.

Known polymer composition (US Pat. RF 2420544, IPC C08K 5/34 (2006.01), C08L 79/06 (2006/01), C09B 47/14 (2006.01) filing date of the application is January 11, 2010, published January 11, 2010, Bull. No. 16 "Polymer composition"). A polymer composition comprising a metal-containing phthalocyanine additive, characterized in that the polymer contains the copolycondensation product of terephthalic and paratoluylic acids and hydrazine sulfate, and the additive is copper hexadecalogenophthalocyanine of the general formula

Where R is Cl or Br, at the following content of components, wt. h

the specified polymer 85-95;

specified additive 15-5.

2. A polymer composition comprising a metal-containing phthalocyanine additive, characterized in that the polymer contains a copolycondensation product of a mixture of terephthalic, isophthalic, paratoluylic, metatoluylic acid and hydrazine sulfate, and the additive is copper hexadecalogenophthalocyanine of the general formula:

Where R is Cl or Br, at the following content of components, parts by weight

the specified polymer 85-95;

specified additive 15-5.

A known method of producing a dope solution for forming a light-resistant polyoxadiazole fiber in a method for producing polyoxadiazole fiber (US Pat. RF 2213815, IPC D01F 6/74 (2000.01), application date 2000.12.29, published 2003.10.10 “Method for producing polyoxadiazole fiber or thread”) including the preparation of a polymer spinning dope by polycondensation by heating hydrazine sulfate with arylendicarboxylic acid in a concentrated sulfuric acid medium containing free sulfuric anhydride, homogenization of the spinning dope by concentration and viscosity, filtration, degassing, spinning of a fiber in a water-sulfuric acid precipitation bath, extraction, extraction on irrigated rollers, washing, neutralizing acid traces and heat treatment, characterized in that terephthalic acid with 0.004-0.017 wt. % paratoluylic acid or a mixture of terephthalic acid and 0.5-99 wt. % isophthalic acid with 0.004-0.017 wt. % mixture of paratoluic acid with 0.5-99 wt. % metatoluylic acid, obtaining a (co) polymer dope is carried out first sequentially loading with constant stirring in concentrated sulfuric acid containing 17-65 wt. % free anhydride, 0.02-22.9 wt. % of the indicated arylendicarboxylic acid, 3.1-27.4 wt. % hydrazine sulfate with 0.05-34 wt. % water and 0.05-21.8 wt. % metaazobenzene dicarboxylic acid or paraazobenzene dicarboxylic acid, or a mixture thereof, or 0.06-25.3 wt. % of their disodium salt, or 0.07-27.8 wt. % of their dipotassium salt, or 0.07-30.4 wt. % mixture of disodium salt of azobenzene dicarboxylic acids with salts of inorganic acids or 0.08-33.4 wt. % of a mixture of a dipotassium salt of azobenzene dicarboxylic acids with salts of inorganic acids, heating the resulting solution with constant stirring to 50-90 ° C for 0.5-1.5 hours, keeping at this temperature for 3-12 hours to obtain 6.0-20, 0% oligomer solution, cooling it to 20-35 ° C at a rate of 0.5-5.0 ° C / min, and then 2-89 wt. % sulfuric acid containing 17-65 wt. % sulfuric anhydride and incubated for 3.0-5.5 hours with constant stirring to obtain a 5.0-14.8% solution of the oligomer, then with constant stirring, conduct (co) polycondensation, heating the solution to 90-160 ° C in flow 0.5-1.5 hours, keeping at this temperature 0.5-3.0 hours, cooling to 60-120 ° C and additionally introducing 3.4-94.2 wt. % sulfuric acid with 6-8 wt. % water, the resulting solution is cooled to 20-35 ° C and constantly stirred for 3.5-5.5 hours to obtain a spinning 3-14% solution of the polymer in sulfuric acid with a viscosity of 2000-6000 poise, degassing is carried out in the apparatus continuous operation for 2-48 hours until the air content in the solution reaches 1-6 ml / l, the spinning solution is fed for molding under a pressure of 7-20 atm into a precipitation bath having a temperature of 30-70 ° C and a density of 0.65 -0.85 of the density of the spinning dope of the polymer, when passing the freshly formed fiber through it for 2-17 s, the hood is carried out 2-6 times in a solution of sulfuric acid with a density exceeding the density of the precipitation bath by 4-14%.

Closest to the claimed is the polymer composition Pat. RF 2427596 IPC C08K 5/34 (2006.01), C08L 79/06 (2006.01), C09B 47/14 2006.01), application filing date 2010.01.11, published 2011.08.27 Bul. No. 24 "Polymer composition (options)).

1. A polymer composition comprising a metal-containing phthalocyanine additive, characterized in that the polymer contains a copolycondensation product of terephthalic and paratoluic acid and hydrazine sulfate, and metaazobenzene dicarboxylic acid, and the additive is copper hexadecalogenophthalocyanine of the general formula: where R = Cl or

At the following content of components, parts by weight:

the specified polymer is 85-95;

the specified additive is 15-5.

2. A polymer composition comprising a metal-containing flococyanine additive, characterized in that the polymer contains a copolycondensation product of a mixture of terephthalic, isophthalic, paratoluylic, metatoluylic acid and hydrazine sulfate, and metaazobenzene dicarboxylic acid, and the additive is a general hexadecalogeno-decalogen:

where R = Cl or Br,

At the following content of components, parts by weight:

the specified polymer is 85-95;

the specified additive is 15-5.

The proposed compositions provide color and light-resistant products with increased fire resistance: the oxygen index is 29.5-32%, but they do not allow the polymer to be formed from which polyocadiazole fibers can be processed into paper using traditional paper technology.

Closest to the claimed is a method of producing a dope in a method for producing polyoxadiazole fiber (US Pat. 015707 IPC D01F 6/74 (2006/01), D01D 5/098 (2006/01), D01D 5/12 (2006/01), date filing application 2007.09.19, published 2011.10.31 “Methods for producing a polyoxadiazole yarn and polyoxadiazole fiber, yarn and fiber obtained by these methods”), in which a polymer dope is obtained, for which sulfuric acid containing 17-65 wt. % free anhydride, then 0.02-22.9 wt. % arylendicarboxylic acid, which is terephthalic acid with 0.004-0.017 wt. % paratoluylic acid or a mixture of terephthalic acid and 0.5-99.0 wt. % isophthalic acid with 0.004-0.017 wt. % mixture of paratoluic acid with 0.5-99.0 wt. % metatoluylic acid, 3.1-27.4 wt. % hydrazine sulfate with 0.05-34.0 wt. % water and 0.05-21.8 wt. % metaazobenzene dicarboxylic acid and / or para-azobenzene dicarboxylic acid, or 0.06-25.3 wt. % of their disodium salt, or 0.07-27.8 wt. % of their dipotassium salt, or 0.07-30.4 wt. % of a mixture of disodium salt of azobenzene dicarboxylic acids with salts of inorganic acids, or 0.08-33.4 wt. % of a mixture of the dipotassium salt of azobenzene dicarboxylic acids with salts of inorganic acids, while the content of the salt of an inorganic acid in its mixture with the disodium or dipotassium salt of azobenzene dicarboxylic acids is 0.5-50.0 wt. %, the resulting solution is heated with constant stirring to 50-90 ° C for 0.5-1.5 hours, maintained at this temperature for 3-12 hours to obtain a 6-20% solution of the oligomer, cooled to 20-35 ° C at a rate of 0.5-5 ° C / min, and then 2-89% sulfuric acid containing 17-65 wt. % sulfuric anhydride, and incubated for 3-5.5 hours with constant stirring to obtain a 5.0-14.8% oligomer solution, then (co) polycondensation is carried out with constant stirring, for which the solution is heated to 90-160 ° C for 0.5-1.5 hours, kept at this temperature for 0.5-3 hours, then cooled to 60-120 ° C and additionally introduced 3.4-94.2 wt. % sulfuric acid with 6-8 wt. % water, continue to cool the resulting solution to 20-35 ° C with constant stirring for 3.5-5.5 hours to obtain a spinning 3-14% solution of the polymer in sulfuric acid with a viscosity of 2000-6000 poise, while ( c) polycondensation is carried out in a continuous manner with continuous dosing of sulfuric acid with 6-8 wt. % water in a spinning solution or in a batch process by introducing sulfuric acid with 6-8 wt. % water in the spinning solution, first in an amount of 0.1-0.5 of the selected, and then the rest with continuous stirring in two or three doses in equal or unequal proportions for 0.5-2 hours, then degassed in a continuous apparatus in for 2-48 hours until the air content in the solution reaches 1-6 ml / l, after which the spinning solution is fed to a spinneret kit containing 1-12 spinnerets with 200-4800 holes in each, and molding is carried out under a pressure of 7-20 atm into a precipitation bath containing concentrated sulfuric acid at a temperature ure 30-70 ° C and a density of 0.65-0.85 of the density of the spinning dope of the polymer when passing the freshly formed fiber through it for 2-17 seconds with drawing 2-6 times, then the resulting freshly formed fiber is washed from traces of sulfuric acid, wring out, oil, corrugate at a temperature of 25-250 ° C and. dried first at a temperature of 190-210 ° C, then at 90-110 ° C and cut into staples, characterized in that the fiber is drawn 2-6 times in air when air is fed along the drawn fibers in the opposite direction to their movement, at a speed of 5.0-5.2 m / min. The polyoxadiazole fiber obtained by this method is characterized by a linear density of elementary fiber of 0.17-0.7 tex, a relative tensile load of 20-35 cN / tex, a relative tensile elongation of 20-60%, shrinkage at a temperature of 350 ° C of 1%, and maintaining strength after aging at a temperature of 350 ° C for 25 hours in the air 85-95%, light fastness 75-90%, color fastness of the dyed fiber 4-6 points, oxygen index 29-31%, the presence of micro roughness and the content on the surface of 0.4-0.6 mmol / g of oxygen-containing groups.

However, this method of producing a dope solution is intended to produce polyoxadiazole fibers or filaments with a high oxygen index and the presence of micro roughness and oxygen groups on the surface of filaments and does not allow to produce synthetic papers with electrostatic properties from the obtained fibers or filaments.

The technical result of the claimed invention is to maintain the speed of molding, dynamic viscosity and concentration of the dope solution with the simultaneous formation of a surface layer of carbon nanoparticles on the obtained filaments when passing through a die for forming synthetic papers with electrostatic properties.

The problem is achieved in that in a polymer composition comprising a metal-containing flocyanine additive, which is copper hexadecalogenophthalocyanine of the general formula: where R = Br,

and the polymer is a copolycondensation product of a mixture of terephthalic, isophthalic, paratoluylic, metatoluylic acid and hydrazine sulfate, and metaazobenzene dicarboxylic acid in an amount of 85-95 wt. h, characterized in that the additive additionally contains carbon nanoparticles with the following content of all components wt.h:

polymer - 85-95;

copper hexadecagalogenophthalocyanine - 14.998-4.999;

carbon nanoparticles - 0.002-0.001.

A method of obtaining a spinning solution based on a polymer composition, which consists in first loading sulfuric acid containing 17-65 wt. % free anhydride, then 0.02-22.9 wt. % arylendicarboxylic acid, which is a mixture of terephthalic acid and 0.5-99.0 wt. % isophthalic acid with 0.004-0.017 wt. % mixture of paratoluic acid with 0.5-99.0 wt. % metatoluylic acid, 3.1-27.4 wt. % hydrazine sulfate with 0.05-34.0 wt. % water and 0.05-21.8 wt. % metaazobenzene dicarboxylic acid, heating the resulting solution with constant stirring to 50-90 ° C for 0.5-1.5 hours, keeping at this temperature for 3-12 hours to obtain a 6-20% solution of the oligomer, cooling it to 20 -35 ° C at a rate of 0.5-5 ° C / min, and then the introduction of 2-89% sulfuric acid containing 17-65 wt. % sulfuric anhydride, and incubation for 3-5.5 hours with constant stirring until a 5.0-14.8% oligomer solution is obtained, then polycondensation is carried out with constant stirring, while heating the solution to 90-160 ° C for 0, 5-1.5 hours, keeping at this temperature for 0.5-3 hours, then cooling to 60-120 ° C and additional introduction of 3.4-94.2 wt. % sulfuric acid with 6-8 wt. % of water, continuing to cool the resulting solution to 20-35 ° C with constant stirring until a spinning 3-14% polymer solution in sulfuric acid with a viscosity of 2000-6000 poises is obtained, while polycondensation is carried out in a continuous way with continuous dosing of sulfuric acid from 6-8 wt. % water in the spinning solution, then conducting degassing in a continuous apparatus for 2-48 hours until the air content in the solution reaches 1-6 ml / l, after which the spinning solution is fed to molding in a known manner, characterized in that in addition to 3, 4-94.2 wt. % sulfuric acid with 6-8 wt. % of water is added to the additive containing copper hexadecagalogenophthalocyanine and carbon nanoparticles, and cooling the obtained dope at a ratio of 85-95 wt. including a polymer, copper hexadecagalogenophthalocyanine 14.998-4.999, carbon nanoparticles 0.002-0.001 with constant stirring on an ultrasonic disperser at a frequency of 24 kHz is carried out for 2.0-2.5 hours

It is known to use carbon nanoparticles introduced into the polymer to harden the polymer. (Ognev, A.Yu., Teplykh, AM Bataev, V.A. Kudashov A.G., Okotrub, A.V. / Polymer composite material based on epoxy resin, hardened by multilayer carbon nanotubes // Scientific Bulletin of NSTU, 2009 ., No. 4 (37), pp. 15-23).

It is known to use carbon nanoparticles to change the electrical conductivity and mechanical properties of polymer composites (Yakovlev E.A., Yakovlev N.A., Ilyinykh I.A., Burmistrov I.N., Gorshkov N.V. / Study of the effect of functionalized multi-walled carbon nanotubes on electrical conductivity and mechanical characteristics of epoxy composites // Tomsk State University Bulletin. Chemistry. 2016. No. 3 (5). P. 15-23)

Thus, only the totality of all indicators, that is, the introduction of additives, with a ratio of 85-95 wt. including polymer, hexadecahalogenophthalocyanine of copper 14.998-4.999, carbon nanoparticles 0.002-0.001 and technology for producing a spinning solution, including continuous mixing on an ultrasonic disperser at a frequency of 24 kHz for 2.0-2.5 hours, allows to maintain the molding speed, dynamic viscosity and the concentration of the spinning solution with the simultaneous formation of a surface layer of carbon nanoparticles on the resulting filaments when passing through a die for forming synthetic papers with electrostatic properties you.

Example 1

In a barque for the preparation of a dope solution, sulfuric acid containing 17-65 wt. % free anhydride, 0.02-22.9 wt. % of the indicated arylendicarboxylic acid, which is terephthalic acid with 0.004-0.017 wt. % paratoluylic acid, 3.1-27.4 wt. % hydrazine sulfate with 0.05-34.0 wt. % water and 0.05-21.8 wt. % metaazobenzene dicarboxylic acid. The initial solution is heated with constant stirring to a temperature of 50-90 ° C for 0.5-1.5 hours, maintained at this temperature for 3-12 hours to obtain a 6-20% solution of the oligomer in sulfuric acid, and cooled to 20 -35 ° C at a rate of 0.5-5 ° C / min. Then, at the second stage, 2-89% sulfuric acid containing 17-65 wt.% Is additionally introduced into a 6-20% solution of the oligomer. % sulfuric anhydride and the solution can withstand 3-5.5 hours with constant stirring to obtain a 5-14.8% solution of the oligomer. Next, the solution with constant stirring is transferred by a gear pump to the polycondensation unit. The solution is heated to 90-160 ° C for 0.5-1.5 hours, keeping at this temperature for 0.5-3 hours, cooled to 60-120 ° C and additionally introduced with a gear pump 3.4-94.2 wt. . % sulfuric acid with 6-8 wt. % water containing the additive in an amount of 14,998 wt. h copper hexadecagalogenophthalocyanine of the general formula: where R = Br,

and 0.002 wt. h of carbon nanoparticles, the polymer content of 85 wt. h. The polymer composition is analyzed for the content of the introduced additives:

polymer - 85;

copper hexadecagalogenophthalocyanine -14.998;

carbon nanoparticles - 0.002.

Then, with constant stirring on an ultrasonic flow disperser at a frequency of 24 kHz for 2.0 hours, continue to cool the resulting solution to 20-35 ° C to obtain a spinning 3-14% solution of the polymer in sulfuric acid with a viscosity of 2000-6000 poise, while polycondensation is carried out in a continuous manner with continuous dosing of sulfuric acid with 6-8 wt. % water with an additive in the amount of 14,998 wt. h of hexadecagalogenophthalocyanine copper and 0.002 wt. h of carbon nanoparticles into a spinning solution, then degassing is carried out in a continuous apparatus for 2-48 hours until the air content in the solution reaches 1-6 ml / l, after which the spinning solution is fed to molding in a known manner.

The polyoxadiazole fiber obtained by this method has the following physical and mechanical properties:

the linear density of the elementary fiber is 0.17-0.7 tex;

relative breaking load - 42 cN / tex;

relative tensile elongation - 20-60%;

shrinkage at a temperature of 350 ° C - 1%;

preservation of strength after exposure at a temperature of 350 ° C for 25 hours in air - 85-95%;

the presence of micro-roughness per 1 mm of length 40;

on filaments, the presence of a surface layer of carbon nanoparticles.

Synthetic paper is produced from the obtained polyoxaziazole fiber, which has electrostatic properties by a technology that includes the following stages: preparation of an aqueous dispersion of cut chemical fibers, dispersion feeding to a paper machine, on which a web is continuously formed from the dispersion by dehydration by mechanical extraction of moisture under pressure and vacuum due to the passage of the web through several roller presses with subsequent compaction of the paper. At this stage, cohesion of the cut fibers occurs due to the layer of carbon nanoparticles formed on the surface of the filaments in the process of forming the fiber. After that, the resulting synthetic paper goes to the finish, where the canvas is subjected to the necessary processing on calendars.

As a result, synthetic paper was obtained, which can be used for the manufacture of a line for supplying bulk electrifying substances, for the manufacture of containers for transporting bulk substances it has the following physical and mechanical properties:

surface density - 80 g / m ² ;

breaking load - 85 N / cm;

tensile elongation - 1.3%;

oxygen index - 32;

shrinkage at 300 ° C - 2.0%.

In addition, it has reduced hygroscopicity, increased heat and biostability, improved electrostatic properties due to the combination of the properties of a synthetic polyoxadiazole fiber and a layer of carbon nanoparticles on the surface of the filaments formed during spinning.

The remaining examples were performed under the conditions of the previously given experiment with a change in the amount of additive and the mixing time.

For all the examples presented in the table, a layer of carbon nanoparticles forms on the surface of the filaments, which is confirmed by the data of an electron microscope photo taken for each sample The use of copper hexadecalogenophthalocyanine, in which Cl is contained as a radical, only leads to a change in the color of the fiber. Figure 1 shows a photograph taken with an electron microscope for a fiber sample obtained in Example 1, where 1 is a fiber that is subsequently cut when receiving synthetic paper; 2 - a layer of carbon nanoparticles.

Claims (8)

1. A polymer composition comprising a metal-containing flococyanine additive, which is copper hexadecagalogenophthalocyanine of the general formula: where R = Br

as a polymer contains the copolycondensation product of a mixture of terephthalic, isophthalic, paratoluylic, metatoluylic acid and hydrazine sulfate, and metaazobenzene dicarboxylic acid in an amount of 85-95 wt. h, characterized in that the additive further comprises carbon nanoparticles in the following components. h: polymer - 85-95; copper hexadecagalogenophthalocyanine - 14.998-4.999; carbon nanoparticles - 0.002-0.001. 2. A method of obtaining a spinning solution based on a polymer composition, which consists in first loading sulfuric acid containing 17-65 wt. % free anhydride, then 0.02-22.9 wt. % arylendicarboxylic acid, which is a mixture of terephthalic acid and 0.5-99.0 wt. % isophthalic acid with 0.004-0.017 wt. % mixture of paratoluic acid with 0.5-99.0 wt. % metatoluylic acid, 3.1-27.4 wt. % hydrazine sulfate with 0.05-34.0 wt. % water and 0.05-21.8 wt. % metaazobenzene dicarboxylic acid, heating the resulting solution with constant stirring to 50-90 ° C for 0.5-1.5 hours, keeping at this temperature for 3-12 hours to obtain a 6-20% solution of the oligomer, cooling it to 20 -35 ° C at a rate of 0.5-5 ° C / min, and then the introduction of 2-89% sulfuric acid containing 17-65 wt. % sulfuric anhydride, and incubation for 3-5.5 hours with constant stirring until a 5.0-14.8% oligomer solution is obtained, then polycondensation is carried out with constant stirring, while heating the solution to 90-160 ° C for 0, 5-1.5 hours, keeping at this temperature for 0.5-3 hours, then cooling to 60-120 ° C and additional introduction of 3.4-94.2 wt. % sulfuric acid with 6-8 wt. % water, continuing to cool the resulting solution to 20-35 ° C with constant stirring until a spinning 13-14% polymer solution in sulfuric acid with a viscosity of 2000-6000 poise is obtained, while polycondensation is carried out in a continuous way with continuous dosing of sulfuric acid from 6-8 wt. % of water in the spinning solution, then degassing is carried out in a continuous apparatus for 2-48 hours until the air content in the solution reaches 1-6 ml / l, after which the spinning solution is fed to molding in a known manner, characterized in that in addition to 3, 4-94.2 wt. % sulfuric acid with 6-8 wt. % of water is injected with an additive containing copper hexadecahalogenophthalocyanine and carbon nanoparticles, and cooling the resulting dope at a ratio of 85-95 wt. including a polymer, copper hexadecagalogenophthalocyanine 14.998-4.999, carbon nanoparticles 0.002-0.001 with constant stirring on an ultrasonic disperser at a frequency of 24 kHz is carried out for 2.0-2.5 hours

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