RU2845756C1 - Method of producing nanocomposite electrically conducting material based on heterocyclic polyazine - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: invention relates to production of novel nanocomposite electrically conducting materials based on polyconjugated polymers and carbon nanomaterials (CNM) and can be used in the electronic equipment components creation, (bio)sensors, sensors, organic solar cells, rechargeable batteries, supercapacitors, biofuel cells, optoelectronic and electrochromic devices, as mediator catalysts and high-efficiency adsorbents of various types of contaminants, such as heavy metal ions and organic dyes, as well as in medicine, in biomedical engineering, in the development of various drug analysers, in drug delivery systems, etc. Described is a method of producing nanocomposite electroconductive material based on a polyconjugated polymer and electroconductive carbon nanomaterial, involving mixing the polyconjugated polymer with CNM, followed by removal of the solvent from the suspension until a nanocomposite electroconductive material is obtained. Polyconjugated polymer used is a heterocyclic polyazine obtained by interphase oxidative polymerisation of a monomer with a sulphur heteroatom-phenothiazine with concentration of monomer [M]=0.1 mol/l and oxidising agent [(NH₄)₂S₂O₈]=0.125 mol/l. Polyazine is mixed with the CNM taken in amount of 1 to less than 5 wt. % relative to the weight of the polymer in the solvent in an ultrasonic bath at room temperature for 0.5 hours to obtain a suspension, and the solvent is removed while gradually raising temperature from 60 to 85 °C to avoid spitting out the suspension.

EFFECT: obtaining nanocomposite material having improved electroconductive properties and heat resistance while simplifying the method of producing said material.

2 cl, 17 dwg, 1 tbl, 16 ex

Description

The invention relates to the field of creating new nanocomposite electrically conductive materials based on polyconjugated polymers and carbon nanomaterials (CNM) and can be used in creating components of electronic equipment, (bio)sensors, detectors, organic solar cells, rechargeable batteries, supercapacitors, biofuel cells, optoelectronic and electrochromic devices, as mediator catalysts and high-performance adsorbents of various types of pollutants, such as heavy metal ions and organic dyes, as well as in medicine, in biomedical engineering, in creating various drug analyzers, in drug delivery systems, etc.

Among carbon materials, graphene oxide (GO) and reduced graphene oxide (RGO) are more economically accessible. Researchers' interest in carbon nanotubes (CNTs) also continues unabated due to their remarkable physicochemical properties, such as high thermal stability and electrical conductivity.

Composite materials are mainly obtained by in situ oxidative polymerization of aniline and other monomers in the presence of GO or CNTs [1-3].

The closest to the proposed invention are a hybrid conductive material based on poly-3-amino-7-methylamino-2-methylphenazine (PAMMP) and single-wall carbon nanotubes (SWCNTs) and a method for producing this composite material by oxidative polymerization of 3-amino-7-dimethyl amino-2-methyl phenazine hydrochloride (neutral red) (ADMPH) in an aqueous solution of acetonitrile under the action of ammonium persulfate in the presence of the initial SWCNTs (d=1.4-1.6 μm, l=0.5-1.5 μm) in a reaction mixture in an amount of 1-10% by weight, based on the weight of the monomer [4]. The resulting hybrid nanomaterial is characterized by high electrical conductivity (6.2×10 ^-4 - 1.8×10 ^-2 S/cm) and thermal stability in air (up to 290-320°C) and in an inert atmosphere (at 1000°C the residue is 45-73%).

The disadvantage of the known material and method is the insufficient increase in electrical conductivity (not higher than 1.8×10 ^-2 S/cm) and thermal stability in air (the temperature at which decomposition begins is not higher than 320°C), as well as the limited solubility of the monomer in the reaction medium to a concentration of 0.01-0.05 mol/l, which complicates its practical use due to the small amount of product obtained.

The objective of the proposed invention is to create a nanocomposite electrically conductive material with high thermal stability (thermostability) and electrical conductivity of the material, as well as to develop an effective environmentally friendly method for its production.

The stated problem is solved by proposing a nanocomposite conductive material based on a thermally stable polyconjugated polymer and a conductive carbon nanomaterial (CNM), according to which the material contains a heterocyclic polyazine of the general structural formula as a thermally stable polyconjugated polymer

where Y is a sulfur or oxygen heteroatom

with the content of electrically conductive carbon nanomaterial (CNM) in the said material in an amount of 1-10% by weight, based on the weight of the polymer.

A heterocyclic polyazine with a sulfur heteroatom is polyphenothiazine (PPTA), and with oxygen it is polyphenoxazine (PFOA).

The proposed nanocomposite electrically conductive material contains an electrically conductive CNM selected from the following series: reduced graphene oxide (RGO), single-wall carbon nanotubes (SWCNT), and multi-wall carbon nanotubes (MWCNT).

The nanocomposite conductive material obtained according to the invention is a black powder that is insoluble in organic solvents.

The heterocyclic polyazines synthesized by the authors are well adsorbed on the CNM surface due to the π-stacking effect and functional groups (heteroatoms N and S(O)). The polymer matrix prevents the aggregation of CNM.

The stated problem is also solved by the fact that an environmentally friendly method for obtaining a nanocomposite conductive material based on a polyconjugated polymer and a carbon nanomaterial (CNM) is proposed, which includes mixing a polyconjugated polymer with a carbon nanomaterial (CNM) followed by removing the solvent from the suspension to obtain a nanocomposite conductive material, in which a heterocyclic polyazine of the general structural formula is used as a polyconjugated polymer

where Y is a sulfur or oxygen heteroatom,

which is mixed with a carbon nanomaterial (CNM), which is graphene oxide (GO), SWCNT or MWCNT, taken in an amount of 1-10% by weight, relative to the weight of the polymer, in a solvent (DMF) in an ultrasonic bath at room temperature for 0.5 h to obtain a suspension, while the solvent is removed by gradually increasing the temperature from 60 to 85 °C to avoid splashing out the thick suspension, to obtain a nanocomposite conductive material based on a polyconjugated polymer (PFTA or PFOA) containing CNM (RGO, SWCNT or MWCNT).

According to the proposed method for obtaining a nanocomposite conductive material, in addition to DMF, DMSO or N-methyl-2-pyrrolidone can be used.

Advantages of the proposed method:

1. The method allows obtaining a heat-resistant (thermostable) electrically conductive nanomaterial based on a polyconjugated polymer (PFTA or PFOA) and CNM (RGO, SWCNT or MWCNT) by mixing the polymer and CNM with subsequent removal of the solvent (DMF) from the suspension without adding chemical reducing agents that can lead to contamination of the final product, which ensures its environmental friendliness.

2. The heterocyclic polyazines - PFTA or PFOA, synthesized by the authors for the first time, are well adsorbed on the surface of CNM due to the π-stacking effect and functional groups (heteroatoms N and S(O)). The polymer matrix prevents the aggregation of CNM.

3. The method allows obtaining a nanomaterial with high electrical conductivity of up to 5.5×10 ^-1 S/cm - 1.7 S/cm. According to the prototype, the conductivity of the material does not exceed 6.2×10 ^-1 S/cm - 1.8×10 ^-2 S/cm. Such nanocomposite conductive materials can be used to create electrochemical devices, (bio)sensors, sensors, supercapacitors, biofuel cells, optoelectronic and electrochromic devices, as mediator catalysts, etc.

4. The obtained nanocomposite material is characterized by high thermal stability. The temperature of the beginning of decomposition of the obtained material in air reaches 430-510°C compared to the prototype (does not exceed 290-320°C). In an argon atmosphere at 1000°C, the residue is 44-64%. High thermal stability of the polymer matrix makes it possible to use the declared CNM/PFTA or CNM/PFOA nanocomposite in the creation of electronic components, organic solar cells, rechargeable batteries, supercapacitors, biofuel cells operated at elevated temperatures.

The following examples illustrate, but do not limit, the proposed invention.

The formation of the CNM/PFTA or CNM/PFOA nanocomposite is confirmed by FTIR spectroscopy and X-ray diffraction data, as well as high-resolution scanning electron microscopy (SEM), shown in Figs. 1–13, where I is the intensity, 20 is the angle, I/I° is the ratio of the intensities of the incident and transmitted radiation, ν is the radiation frequency.

Fig. 1 shows the IR spectra (ATR) of PFTA (1) and nanocomposites of RGO/PFTA (2), SWCNT/PFTA (3) and MUSh7PFTA (4), obtained from a polymer solution in DMF at [CNT]=10% by weight, relative to the polymer weight.

Fig. 2 shows the IR spectra (ATR) of PFOA (1) and nanocomposites of RGO/PFOA (2), SWCNT/PFOA (3) and MWCNT/PFOA (4), obtained from a polymer solution in DMF at [CNT] - 10% by weight, relative to the polymer weight.

Fig. 3 shows the diffraction patterns of PFTA (1) and nanocomposites of SWCNT/PFTA (2) and MWCNT/PFTL (3), obtained from a polymer solution in DMF at [CNT]=10% by weight, relative to the polymer weight.

Fig. 4 shows the diffraction patterns of PFOA (1) and nanocomposites of SWCNT/PFOA (2) and MWCNT/PFOL (3), obtained from a polymer solution in DMF at [CNT]=10% by weight, relative to the polymer weight.

Fig. 5 shows the diffraction patterns of GO (1), RGO/PFTA (2) and RGO/PFOA (3), obtained from a polymer solution in DMF at [GO]=10% by weight, relative to the polymer weight.

Fig. 6 shows the SEM image of PFTA.

Fig. 7 shows the SEM image of PFOA.

Fig. 8 shows the SEM image of the RGO/PFTA nanocomposite obtained from a polymer solution in DMF at [GO]=10% by weight, relative to the polymer weight.

Fig. 9 shows the SEM image of the SWNT/PFTA nanocomposite obtained from a polymer solution in DMF at [WNT]=10% by weight, relative to the polymer weight.

Fig. 10 shows the SEM image of the MWCNT/PPTA nanocomposite obtained from a polymer solution in DMF at [MWCNT]=10% by weight, relative to the polymer weight.

Fig. 11 shows the SEM image of the RGO/PFOA nanocomposite obtained from a polymer solution in DMF at [OG]=10% by weight, relative to the polymer weight.

Fig. 12 shows the SEM image of the SWNT/PFOA nanocomposite obtained from a polymer solution in DMF at [WNT]=10% by weight, relative to the polymer weight.

Fig. 13 shows the SEM image of the MWCNT/PFOA nanocomposite obtained from a polymer solution in DMF at [MWCNT] = 10 wt%, relative to the polymer weight.

Explanations for Figs. 1-13.

In PFTA and PFOA, the growth of the polymer chain occurs by the C-C addition type in the para-position of the phenyl rings relative to nitrogen [5, 6].

In the FTIR spectrum of PFTA, the absorption bands at 865 and 825 cm ^-1 are due to out-of-plane deformation vibrations of the ν _C-H bonds of the 1,2,4-substituted benzene ring (Fig. 1). The absorption bands at 1304 and 1230 cm ^-1 are due to the stretching vibrations of the ν C- _{H bonds.} The intense bands at 1589 and 1461 cm ^-1 are due to the stretching vibrations of the ν _C-C bonds in the aromatic rings. The shift of these absorption bands in the IR spectra of nanocomposites with CNM indicates the π-π interaction of the polymer component with CNM (stacking effect).

The FTIR spectrum of PFOA shows an absorption band at 3380 cm ^-1 , which corresponds to the stretching vibrations of the ν _C-H bonds in the phenoxazine structures. The band around 3055 cm ^-1 in the polymer is due to the stretching vibrations of the ν _C-H bonds of the benzene ring. The bands at 1587 and 1482 cm ¹ correspond to the stretching vibrations of the ν _C-C bonds in the aromatic rings. The absorption band at 1320 cm ^-1 is due to the stretching vibrations of the ν _C -H bonds. The bands in the region of 873 and 808 cm ^-1 are due to out-of-plane deformation vibrations of the δ _C-H bonds of the 1,2,4-substituted benzene ring. The band at 737 cm ^-1 is related to non-planar deformation vibrations of the δ _C-H bonds of the 1,2-substituted benzene ring of the end groups (Fig. 2). All the main bands characterizing the chemical structure of PFOA are preserved in the IR spectra of CNM/PFOA.

The IR spectra are recorded in the surface reflection mode (ATR) using a HYPERION-2000 IR microscope coupled with a Bruker IFS 66v IR Fourier spectrometer in the range of 4000-600 cm ^-1 (scan 150, ZnSe crystal, resolution 2 cm ^-1 ).

The XRF data confirm the formation of nanocomposites based on PFTA or PFOA with CNM (Figs. 3-5). The broad halo recorded for the nanomaterials indicates the amorphous structure of the polymer component.

The diffraction patterns of the MWCNT/PFTA and MWCNT/PFOA nanocomposites contain a reflection peak of the carbon phase at 20=39.17°, which characterizes MWCNT. The absence of a reflection peak of the carbon phase in the diffraction patterns of SWCNT/PFTA and SWCNT/PFOA is explained by the impossibility of obtaining a diffraction pattern from a single plane of SWCNT. The electrical conductivity of CNT-based nanocomposites reaches σ=(8.1×10 ^-1 -1.7) S/cm (Table 1). The specific electrical conductivity of the samples is measured by the standard four-point method on a Loresta-GP, MCP-T610 device (Japan). X-ray diffraction studies are carried out at room temperature on a Diffray-401 X-ray diffractometer with Bragg-Brentano focusing on CrK _α -radiation.

The diffraction patterns of the RGO/PFTA and RGO/PFOA nanocomposites (Fig. 5) do not show a sharp peak at 20=17.08°, which characterizes GO. During the synthesis of the nanocomposites, GO is reduced to form RGO, which is also indicated by the electrical conductivity values (Table 1). The diffraction patterns of the nanocomposites obtained from a polymer solution (PFTA or PFOA) in DMF containing 10% by weight of GO show a broad peak at 20=38.92°, which characterizes RGO. The electrical conductivity of RGO-based nanocomposites reaches σ=(5.5×10 ^-1 -1.1) S/cm, which is comparable with the electrical conductivity of CNT/PFTA and CNT/PFOA, while for the original polymers σ=2.04×10 ^-9 S/cm (PFTA) and 2.80×10 ^-10 S/cm (PFOA). The specific electrical conductivity of the samples is measured by the standard four-point method on a Loresta-GP, MCP-T610 device (Japan).

It should be noted that the reduction of OG under the conditions of preparation of nanocomposites by mixing the polymer and OG in DMF followed by heating at 60-85°C in air to remove the solvent can occur with the participation of the products of partial decomposition of both oligomers and DMF.

The morphology of the nanocomposites in comparison with the initial polymers was studied by high-resolution scanning electron microscopy (SEM), the images of which are shown in Figs. 6-13. According to the SEM data, in the CNM/PFTA and CNM/PFOA nanocomposites, the carbon nanoparticles (RGO, SWCNT and MWCNT) are distributed in the amorphous polymer matrix. Electron microscopic studies were carried out on a Supra 25 scanning electron field emission microscope manufactured by Zeiss with an INCA Energy X-ray spectral energy dispersive attachment manufactured by Oxford Instruments to determine the elemental composition of the samples. The resolution of the obtained images was 1-2 nm.

Thermal stability of CNM/PFTA and CNM/PFOA nanocomposites was studied by TGA and DSC methods.

Fig. 14 shows TGA thermograms of PFTA (1, 2) and RGO/PFTA (3, 4), obtained from a polymer solution in DMF at [OG]=3% by weight, relative to the polymer weight (3, 4), upon heating to 1000°C at a rate of 10°C/min in air (1, 3) and in an argon flow (2, 4).

Fig. 15 shows TGA thermograms of PFOA (1, 2) and RGO/PFOA (3, 4), obtained from a polymer solution in DMF at [OG]=10% by weight, relative to the polymer weight (3, 4), upon heating to 1000°C at a rate of 10°C/min in air (1, 3) and in an argon flow (2, 4).

Fig. 16 shows the DSC thermograms of PFTA (1) and RGO/PFTA (2, 3), obtained from a polymer solution in DMF at [OG]=3% by weight relative to the polymer weight, when heated in a nitrogen flow to 350°C at a rate of 10°C/min (1, 2 - first heating, 3 - second heating).

Fig. 17 shows the DSC thermograms of PFOA (1) and RGO/PFOA (2, 3), obtained from a solution of the polymer in DMF at [OG] = 10% by weight, relative to the polymer weight, when heated in a nitrogen stream to 350°C at a rate of 10°C/min (1, 2 - first heating, 3 - second heating).

As can be seen from Fig. 14 and 15, the high thermal stability of the nanocomposites is determined by the thermal stability of the original polymers. According to the DSC data, the weight loss at low temperatures is associated with the removal of moisture. In an inert environment above 470-480°C, the weight loss of CNM/PFTA and CNM/PFOA occurs gradually. In RGO/PFTA and RGO/PFOA at 1000°C in an inert atmosphere, the residue is 55 and 44%, respectively. RGO/PFOA loses half of the initial weight in an inert atmosphere at 912°C. The processes of thermal-oxidative destruction begin in RGO/PFTA and RGO/PFOA at 490 and 430°C, and in SWCNT/PAMMF (according to the prototype) - at 290°C. In air, 50% weight loss of RGO/PFTA and RGO/PFOA is observed at 559 and 557°C, and for SWCNT/PAMMF (according to the prototype) - at 520°C. Thermal analysis is carried out on a TGA/DSC1 device from Mettler Toledo in a dynamic mode in the range of 30-1000°C in air and in an argon flow. The polymer sample is 100 mg, the heating rate is 10°C/min, the argon flow is 10 ml/min. Calcined aluminum oxide is used as a standard. The analysis of the samples is carried out in an A1 ₂ O ₃ crucible. DSC analysis is carried out on a DSC823 ^e calorimeter from Mettler Toledo. The samples are heated at a rate of 10°C/min, in a nitrogen atmosphere with a feed rate of 70 ml/min. The measurement results are processed using the STARe service program supplied with the device.

By mixing a polymer (PFTA or PFOA) and CNM (GO, SWCNT or MWCNT) with subsequent removal of the solvent (DMF, DMSO or N-methyl-2-pyrrolidone), a heat-resistant (thermostable) electrically conductive nanomaterial CNM/PFTA or CNM/PFOA is formed from the suspension.

The electrical conductivity of the CNM/PFTA or CNM/PFOA nanomaterial is higher than the conductivity of the SWCNT/PAMM nanocomposite (according to the prototype, it does not exceed 6.2×10 ^-4 S/cm-1.8×10 ^-2 S/cm) and depends on the quantitative content of CNM. The electrical conductivity of the CNM/PFTA or CNM/PFOA nanomaterial ranges from 5.5×10 ^-1 S/cm to 1.7 S/cm, depending on the synthesis conditions.

Nanocomposites CNM/PFTA or CNM/PFOA have high thermal stability in air and inert atmosphere, comparable to thermal stability of nanocomposite SWCNT/PAMMF (according to the prototype). In CNM/PFTA or CNM/PFOA in argon atmosphere at 1000°C the residue is 44-64%, and the temperature of the onset of decomposition in air is significantly higher and reaches 430-510°C compared to the prototype (does not exceed 290-320°C).

The technical result that can be achieved from the proposed invention consists in obtaining a nanocomposite material with electrically conductive properties, increasing the electrical conductivity to 5.5×10 ^-1 S/cm - 1.7 S/cm compared to the prototype (does not exceed 6.2×10 ^-4 S/cm - 1.8×10 ^-2 S/cm) and heat resistance (thermostability) (the temperature of the onset of decomposition in air reaches 430-510°C) of the obtained material compared to the prototype (does not exceed 290-320°C), while simplifying the method for its production and environmental friendliness.

The following examples illustrate the proposed technical solution, but do not limit it in any way.

Example 1

To synthesize the SWCNT/polyphenothiazine nanocomposite according to the proposed method, polyphenothiazine (PPTA) with the structural formula is used as a polymer

In a 50 ml crystallization dish, a solution of PFTA (0.1 g) is prepared in DMF (10 ml), additionally containing SWCNT (0.01 g) (10% by weight, relative to the polymer weight). The finished polymer obtained by the method described in work (5) is used. PFTA was obtained by interfacial oxidative polymerization ([PTA] = 0.1 mol/l, [(NH ₄ ) ₂ S ₂ O ₈ ] = 0.125 mol/l).

The resulting suspension of SWCNTs/PFTA in DMF is stirred in an ultrasonic bath at room temperature for 0.5 h. The SWCNTs/PFTA nanocomposite is obtained by removing the solvent (DMF) by gradually increasing the temperature from 60 to 85°C to avoid splashing out the thick suspension.

The yield of the initial SWCNT/PPTA nanocomposite obtained by the proposed method is 0.103 g (93.64%) at [SWCNT]=10% by weight.

The characteristics and properties of the nanocomposite material obtained from the example: the content of SWCNTs, heat resistance (thermostability) and electrical conductivity are given in Table 1.

Example 2

The method for obtaining a nanocomposite is carried out similarly to example 1, but for the synthesis of SWCNT/polyphenoxazine according to the proposed method, polyphenoxazine (PFOA) of the structural formula is taken as a polymer

0.1 g of PFOA is dissolved in DMF (10 ml) and 0.01 g of SWCNTs (10% by weight, relative to the polymer weight) are added. The finished polymer obtained by the method described in work (6) is used. PFOA was obtained by interfacial oxidative polymerization ([FOA]=0.1 mol/l, [(NH ₄ ) ₂ S ₂ O ₈ ]=0.125 mol/l).

The characteristics and properties of the nanocomposite material obtained from the example: the content of SWCNTs, heat resistance (thermostability) and electrical conductivity are given in Table 1.

Example 3

The method for obtaining a nanocomposite is carried out similarly to example 1, but 0.01 g of MWCNTs are taken (10% by weight, relative to the weight of the polymer).

The characteristics and properties of the nanocomposite material obtained from the example: MWCNT content, heat resistance (thermostability) and electrical conductivity are given in Table 1.

Example 4

The method for obtaining a nanocomposite is carried out similarly to example 1, but 0.003 g of OG is taken (3% by weight, relative to the weight of the polymer).

The characteristics and properties of the nanocomposite material obtained from the example: GO content, heat resistance (thermostability) and electrical conductivity are given in Table 1.

Example 5

The method for obtaining a nanocomposite is carried out similarly to example 2, but 0.01 g of MWCNTs are taken (10% by weight, relative to the mass of the polymer).

The characteristics and properties of the nanocomposite material obtained from the example: MWCNT content, heat resistance (thermostability) and electrical conductivity are given in Table 1.

Example 6

The method for obtaining a nanocomposite is carried out similarly to example 2, but 0.01 g of OG is taken (10% by weight, relative to the weight of the polymer).

The characteristics and properties of the nanocomposite material obtained from the example: GO content, heat resistance (thermostability) and electrical conductivity are given in Table 1.

Example 7

The method for obtaining a nanocomposite is carried out similarly to example 1, but 0.003 g of SWCNTs are taken (3% by weight, relative to the mass of the polymer).

The characteristics and properties of the nanocomposite material obtained from the example: the content of SWCNTs, heat resistance (thermostability) and electrical conductivity are given in Table 1.

Example 8

The method for obtaining a nanocomposite is carried out similarly to example 1, but 0.012 g of SWCNTs are taken (1% by weight, relative to the mass of the polymer).

The characteristics and properties of the nanocomposite material obtained from the example: the content of SWCNTs, heat resistance (thermostability) and electrical conductivity are given in Table 1.

Example 9

The method for obtaining a nanocomposite is carried out similarly to example 1, but 0.003 g of MWCNTs are taken (3% by weight, relative to the weight of the polymer).

The characteristics and properties of the nanocomposite material obtained from the example: MWCNT content, heat resistance (thermostability) and electrical conductivity are given in Table 1.

Example 10

The method for obtaining a nanocomposite is carried out similarly to example 2, but 0.003 g of SWCNTs are taken (3% by weight, relative to the mass of the polymer).

The characteristics and properties of the nanocomposite material obtained from the example: the content of SWCNTs, heat resistance (thermostability) and electrical conductivity are given in Table 1.

Example 11

The method for obtaining a nanocomposite is carried out similarly to example 2, but 0.003 g of MWCNTs are taken (3% by weight, relative to the mass of the polymer).

The characteristics and properties of the nanocomposite material obtained from the example: MWCNT content, heat resistance (thermostability) and electrical conductivity are given in Table 1.

Example 12

The method for obtaining a nanocomposite is carried out similarly to example 2, but 0.008 g of MWCNTs are taken (8% by weight, relative to the mass of the polymer).

The characteristics and properties of the nanocomposite material obtained from the example: MWCNT content, heat resistance (thermostability) and electrical conductivity are given in Table 1.

Example 13

The method for obtaining a nanocomposite is carried out similarly to example 1, but 0.002 g of OG is taken (2% by weight, relative to the weight of the polymer).

The characteristics and properties of the nanocomposite material obtained from the example: GO content, heat resistance (thermal stability) and electrical conductivity are given in Table 1.

Example 14

The method for obtaining a nanocomposite is carried out similarly to example 2, but 0.001 g of SWCNTs are taken (1% by weight, relative to the mass of the polymer).

The characteristics and properties of the nanocomposite material obtained from the example: the content of SWCNTs, heat resistance (thermostability) and electrical conductivity are given in Table 1.

Example 15

The method for obtaining a nanocomposite is carried out similarly to example 1, but 0.005 g of OG is taken (5% by weight, relative to the weight of the polymer).

The characteristics and properties of the nanocomposite material obtained from the example: GO content, heat resistance (thermostability) and electrical conductivity are given in Table 1.

Example 16

The method for obtaining a nanocomposite is carried out similarly to example 1, but 0.01 g of OG is taken (10% by weight, relative to the weight of the polymer).

The characteristics and properties of the nanocomposite material obtained from the example: GO content, heat resistance (thermal stability) and electrical conductivity are given in Table 1.

Thus, the proposed invention makes it possible to obtain a heat-resistant (thermostable) electrically conductive nanomaterial for the first time based on a heterocyclic polyazine with a sulfur heteroatom - polyphenothiazine (PPTA) and with an oxygen heteroatom - polyphenoxazine (PFOA) and CNM (RGO, SWCNT or MWCNT) by mixing the polymer and CNM with subsequent removal of the solvent (DMF) from the suspension. The absence of additional chemical reducing agents that can lead to contamination of the final product ensures the environmental friendliness of the claimed method. Heterocyclic polyazines - PPTA or PFOA are well adsorbed on the surface of CNM due to the π-stacking effect and functional groups (N and S(O) heteroatoms). The polymer matrix prevents CNM aggregation. The method makes it possible to obtain a nanomaterial with high electrical conductivity of up to 5.5×10 ^-1 S/cm - 1.7 S/cm. According to the prototype, the conductivity of the material does not exceed 6.2×10 ^-4 S/cm - 1.8×10 ^-2 S/cm.

Sources of information taken into account:

1. Jiang Y., Ji J., Huang L., He C, Zhang J., Wang X., Yang Y. One-pot mechanochemical exfoliation of graphite and in situ polymerization of aniline for the production of graphene/polyanilinc composites for high-performance supercapacitors. // RSC Adv. 2020. 10. 44688-44698. https://doi.org/10.1039/D0RA08450F

2. Suckeveriene R.Y., Zelikman E., Mechrez G., Tzur A., Frisman I., Cohen Y., Narkis M. Synthesis of hybrid polyaniline/carbon nanotube nanocomposites by dynamic interfacial inverse emulsion polymerization under sonication. // J. Appl. Polym. Sci. 2011. V. 120. No. 2. P. 676-682.

3. Mudila H., Zaidi M.G.H., Rana S., Joshi Y., Alam S. Enhanced electrocapacitive performance of graphene oxide polypyrrole nanocomposites. //Int. J. Chem. Analyt. Sci. 2013. 4. 139-145. https://doi.Org/10.1016/j.ijcas.2013.09.001

4. Ozkan S.Zh., Karpacheva G.P. Hybrid material based on poly-3-amino-7-methylamino-2-methylphenazine and single-walled carbon nanotubes and a method for producing it. Russian Federation Patent No. 2635606 C2; published 11/14/2017. BI No. 32.

5. Ozkan S.Zh., Bondarenko G.N., Orlov A.V., Karpacheva G.P. Interfacial oxidative polymerization of phenothiazine. // High-molecular Compounds. B. 2009. Vol. 51.№5. P. 855-863.

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Claims (4)

1. A method for producing a nanocomposite conductive material based on a polyconjugated polymer and a conductive carbon nanomaterial (CNM), comprising mixing the polyconjugated polymer with the CNM, followed by removing the solvent from the suspension until the nanocomposite conductive material is obtained, characterized in that heterocyclic polyazine obtained by interfacial oxidative polymerization of a monomer with a sulfur heteroatom - phenothiazine at a monomer concentration of [M] = 0.1 mol/l and an oxidizer of [(NH ₄ ) ₂ S ₂ O ₈ ] = 0.125 mol/l is used as a polyconjugated polymer, wherein the polyazine is mixed with CNM, taken in an amount of 1 to less than 5 wt.% relative to the weight of the polymer, in a solvent in an ultrasonic bath at room temperature for 0.5 h to obtain a suspension, and the solvent is removed by gradually increasing the temperature from 60 to 85°C to avoid splashing out the suspension, to obtain a nanocomposite conductive material. 2. A method for producing a nanocomposite electrically conductive material according to claim 1, characterized in that it contains an electrically conductive carbon nanomaterial (CNM) selected from the series: reduced graphene oxide (RGO), single-wall carbon nanotubes (SWCNT), multi-wall carbon nanotubes (MWCNT).