RU2845758C1 - 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, biosensors, 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 carbon nanomaterial, involving production of a polyconjugated heterocyclic polyazine based on phenothiazaine or phenoxazine monomers in the presence of carbon nanomaterial. Method comprises first mixing a monomer in a solution of a mixture of toluene and isopropyl alcohol, taken in volume ratio of 1.5:1.0 together with carbon nanomaterial, taken in amount of 1 to less than 5 wt. % relative to weight of monomer – organic phase, mixing is carried out in an ultrasonic bath at room temperature until a homogeneous suspension of the organic phase forms. Method then includes adding to obtained suspension an aqueous solution of ammonium persulphate – aqueous phase, taken with volume ratio of aqueous and organic phases of 1:2, then performing interphase oxidative polymerisation in situ at temperature 15 °C for at least three hours, the reaction mixture is precipitated twice: first, in 5-fold excess of a mixture of methanol and distilled water, taken in a volume ratio of 1.5:1, and then into a double excess of isopropyl alcohol, further filtering the obtained product, washing with distilled water to a colourless filtrate and drying to constant mass to obtain an electrically conductive material.

EFFECT: obtaining nanocomposite material having high electroconductivity and heat resistance while simplifying the method of producing said material due to high solubility of the monomer.

2 cl, 15 dwg, 1 tbl, 15 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 is 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-dimethylamino-2-methylphenazine 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 nm, 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 based on a heterocyclic polyazine with high thermal stability (thermostability) and electrical conductivity of the material, as well as to develop an effective method for its production.

The stated problem is solved by the fact that a method is proposed for obtaining a nanocomposite conductive material based on a polyconjugated polymer and a carbon nanomaterial (CNM), including obtaining a polyconjugated polymer containing CNM, in which a heterocyclic polyazine obtained by interfacial oxidative polymerization of a monomer of the general structural formula is used as a polyconjugated polymer

where Y in polyazine and in the monomer is a sulfur or oxygen heteroatom,

wherein first the monomer is mixed in a solution of a mixture of toluene and isopropyl alcohol, at a volume ratio of 1.5: 1.0, together with a carbon nanomaterial (CNM), taken in an amount of 1-10% by weight, relative to the mass of the monomer, to obtain an organic phase,

mixing is carried out in an ultrasonic bath at room temperature until a homogeneous suspension of the organic phase is formed,

then an aqueous solution of ammonium persulfate is added to the resulting suspension - the aqueous phase, taken at a ratio of the volumes of the aqueous and organic phases of 1:2,

and carry out interphase oxidative polymerization in situ at a temperature of 15°C for at least three hours,

the reaction mixture is precipitated twice: first in a 5-fold excess of a mixture of methanol and distilled water, taken in a volume ratio of 1.5:1.0, and then in a two-fold excess of isopropyl alcohol;

The resulting product is then filtered, washed with distilled water until the filtrate is colorless, and dried in a desiccator with KOH under vacuum until constant weight is reached, yielding a nanocomposite conductive material based on a polyconjugated polymer (PFTA or PFOA) containing CNM (RGO, SWCNT or MWCNT).

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

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

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) in an interphase process.

2. The use of the method of interfacial oxidative polymerization developed by the authors for the formation of CNM/PFTA or CNM/PFOA makes it possible to obtain a nanocomposite material with a high amount of the resulting product due to an increase in the solubility of the monomer by varying the organic solvents to a concentration of 0.1-0.2 mol/l compared to the prototype (does not exceed 0.01-0.05 mol/l).

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

4. The method allows to obtain a nanomaterial with high electrical conductivity up to 5.1 × 10 ^-2 S/cm - 9.2 × 10 ^-2 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. 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.

5. The obtained nanocomposite material is characterized by high thermal stability. The temperature of the onset of decomposition of the obtained material in air reaches 410-550°C compared to the prototype (does not exceed 290-320°C). In an argon atmosphere at 1000°C, the residue is 44-60%. 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, 1/1° is the ratio of the intensities of the incident and transmitted radiation, and v is the radiation frequency.

Figure 1 shows the IR spectra (ATR) of PFTA (1) and nanocomposites of RGO/PFTA (2), SWCNT/PFTA (3) and MWCNT/PFTA (4), obtained by oxidative polymerization at [CNT] = 10% by weight, relative to the monomer weight.

Figure 2 shows the IR spectra (ATR) of PFOA (1) and nanocomposites of RGO/PFOA (2), SWCNT/PFOA (3) and MWCNT/PFOA (4), obtained by oxidative polymerization at [CNT] = 10% by weight, relative to the monomer weight.

Figure 3 shows the diffraction patterns of PFTA (1) and nanocomposites of SWCNT/PFTA (2) and MWCNT/PFTA (3), obtained by oxidative polymerization at [CNT] = 10% by weight, relative to the mass of the monomer.

Figure 4 shows the diffraction patterns of PFOA (1) and nanocomposites of SWCNT/PFOA (2) and MWCNT/PFOA (3), obtained by oxidative polymerization at [CNT] = 10% by weight, relative to the mass of the monomer.

Figure 5 shows the diffraction patterns of GO (1), RGO/PFTA (2) and RGO/PFOA (3), obtained by oxidative polymerization at [GO] = 10% by weight, relative to the monomer weight.

Fig. 6 shows the SEM image of PFTA.

Fig. 7 shows the SEM image of PFOA.

Figure 8 shows the SEM image of the RGO/PFTA nanocomposite obtained by oxidative polymerization at [GO] = 10% by weight, relative to the monomer weight.

Figure 9 shows the SEM image of the SWNT/PPTA nanocomposite obtained by oxidative polymerization at [WNT] = 10% by weight, relative to the monomer weight.

Figure 10 shows the SEM image of the MWCNT/PPTA nanocomposite obtained by oxidative polymerization at [MWCNT] = 10% by weight, relative to the monomer weight.

Figure 11 shows the SEM image of the RGO/PFOA nanocomposite obtained by oxidative polymerization at [GO] = 10% by weight, relative to the monomer weight.

Figure 12 shows the SEM image of the SWNT/PFOA nanocomposite obtained by oxidative polymerization at [WNT] = 10% by weight, relative to the monomer weight.

Figure 13 shows the SEM image of the MWCNT/PFOA nanocomposite obtained by oxidative polymerization at [MWCNT] = 10% by weight, relative to the monomer 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 882 and 817 cm ^-1 are due to out-of-plane deformation vibrations of the v _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 v _CN bonds. The intense bands at 1581 and 1461 cm ^-1 are due to the stretching vibrations of the c _CC 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 V _NH bonds in the phenoxazine structures. The band near 3055 cm ^-1 in the polymer is due to the stretching vibrations of the V _CH bonds of the benzene ring. The bands at 1587 and 1482 cm ^-1 correspond to the stretching vibrations of the v _CC bonds in the aromatic rings. The absorption band at 1321 cm ^-1 is due to the stretching vibrations of the V _CN bonds. The bands in the region of 873 and 808 cm ^-1 are due to the 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 due to the out-of-plane deformation vibrations of the δ _CH bonds of the 1,2-substituted benzene ring of the end groups (Fig. 2). In the IR spectra of CNM/PFOA, all the main bands characterizing the chemical structure of PFOA are preserved.

Registration of RJ spectra in the surface reflection mode (ATR) is performed on 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 XRD data confirm the formation of nanocomposites based on PFTA or PFOA with CNM (Figs. 3-5). The wide halo registered 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 = (10 ^-2 - 10 ^-1 ) 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 2θ = 17.08°, which characterizes GO. During the synthesis of the nanocomposites, GO is reduced to form RGO, which is also evidenced by the electrical conductivity values (Table 1).

According to XRD data, it was found that during the oxidative polymerization of FTA or FOA in the presence of GO, it is reduced to form RGO (Fig. 5). A peak appears at 2θ = 38.92°, characterizing RGO. Probably, during the synthesis of nanocomposites, GO acts as an oxidizer, while being reduced itself. The electrical conductivity of RGO/PFTA and RGO/PFOA nanocomposites reaches σ = 10 ^-2 S/cm, which is comparable with the electrical conductivity of CNT/PFTA and CNT/PFOA, whereas for the original polymers PFTA and PFOA σ = 10 ^-10 S/cm.

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 presented 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 an amorphous polymer matrix. Electron microscopic studies are 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 is 1-2 nm.

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

Figure 14 shows the TGA thermograms of PFTA (1, 2), SWCNT/PFTA (3, 4) and MWCNT/PFTA (5, 6), obtained at [CNT] = 3% by weight, relative to the monomer weight (3-6), upon heating to 1000°C at a rate of 10°C/min in air (1, 3, 5) and in an argon flow (2, 4, 6).

Figure 15 shows TGA thermograms of PFOA (1, 2), SWCNT/PFOA (3, 4) and MWCNT/PFOA (5, 6), obtained at [CNT] = 3% by weight, relative to the monomer weight (3-6), upon heating to 1000°C at a rate of 10°C/min in air (1, 3, 5) and in an argon flow (2, 4, 6).

According to DSC data, the mass loss at low temperatures is associated with moisture removal. In an inert environment above 480°C, the mass loss of CNTs/PFTA occurs gradually. In SWCNTs/PFTA obtained at [SWCNTs]=3% by weight, the residue is 53% at 1000°C. MWCNTs/PFTA loses half of the initial mass in an inert atmosphere at 904°C. The processes of thermal-oxidative destruction begin in CNTs/PFTA at 410-530°C, and in SWCNTs/PAMMF (according to the prototype) - at 290°C. In air, 50% mass loss of CNTs/PFTA is observed at 582°C, and for PFTA and SWCNTs/PAMMF (according to the prototype) - at 541 and 520°C, respectively.

In an inert environment, a gradual mass loss occurs in SWCNT/PFOA and MWCNT/PFOA above 590°C and 560°C, respectively. In SWCNT/PFOA obtained at [SWCNT] - 3% by weight, the residue is 49% at 1000°C, and in MWCNT/PFOA - 53%. SWCNT/PFOA loses half of its initial mass in an inert atmosphere at 969°C. The processes of thermo-oxidative destruction in CNT/PFOA begin at 460°C, and in SWCNT/PAMMF (according to the prototype) - at 290°C. In air, a 50% loss of mass of SWCNT/PFOA and MWCNT/PFOA is observed at 576 and 584°C, respectively, and for PFOA and SWCNT/PAMMF (according to the prototype) - at 578 and 520°C.

Thermal analysis is carried out on a TGA/DSC1 device by Mettler Toledo in 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 samples are analyzed in an Al ₂ O ₃ crucible. DSC analysis is carried out on a DSC823 ^e calorimeter by Mettler Toledo. The samples are heated at a rate of 10°C/min, in a nitrogen atmosphere with a nitrogen supply of 70 ml/min. The measurement results are processed using the STARe service program supplied with the device.

Under conditions of interfacial oxidative polymerization of the monomer (PTA or FOA) in the presence of CNM (GO, SWCNT or MWCNT), a heat-resistant (thermostable) electrically conductive nanomaterial CNM/PFTA or CNM/PFOA is formed.

The electrical conductivity of the CNM/PFTA or CNM/PFOA nanomaterial is higher than the conductivity of the SWCNT/PAMMF 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 5.1 × 10 ^-2 S/cm to 9.2 × 10 ^-2 S/cm, depending on the synthesis conditions.

Nanocomposites CNM/PFTA or CNM/PFOA have high thermal stability in air and in an inert atmosphere, comparable to the thermal stability of the nanocomposite SWCNT/PAMMF (according to the prototype). In CNM/PFTA or CNM/PFOA in an argon atmosphere at 1000°C, the residue is 44-60%, and the temperature of the onset of decomposition in air is significantly higher and reaches 410-550°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, in increasing the electrical conductivity to 5.1 × 10 ^-2 S/cm - 9.2 × 10 ^-2 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 410-550 °C) of the obtained material compared to the prototype (does not exceed 290-320 °C), while simplifying the method for obtaining it due to increasing the solubility of the monomer to a concentration of 0.1-0.2 mol/l compared to the prototype (does not exceed 0.01-0.05 mol/l).

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, phenothiazine (PTA) with the structural formula is taken as a monomer

in the amount of 0.1 mol/l (1.2 g) FTA is dissolved in a mixture of toluene (24 ml) and isopropyl alcohol (16 ml).

Then, 10% by weight of SWCNT relative to the weight of the monomer (0.12 g) is added to the resulting FTA solution.

The resulting SWCNT/PTA suspension is stirred in an ultrasonic bath at room temperature for 0.5 h.

Then, to carry out in situ interfacial oxidative polymerization of PTA in the presence of SWCNTs, an aqueous solution (20 ml) of ammonium persulfate (0.125 mol/l, 1.71 g) is immediately added to the SWCNT/PTA suspension in a mixture of toluene (24 ml) and isopropyl alcohol (16 ml), which forms the organic phase, without gradual dosing of reagents, to form an aqueous phase. The ratio of the volumes of the organic and aqueous phases is 2: 1 ( _Vtotal = 60 ml). The synthesis is carried out for 3 h with vigorous stirring at 15°C. Upon completion of the synthesis, the reaction mixture is precipitated first in a 5-fold excess of a mixture of methyl alcohol and distilled water in a volume ratio of 1.5: 1.0, then in isopropyl alcohol (400 ml);

The resulting product is filtered, washed repeatedly with distilled water to remove residual reagents and dried under vacuum over a COC to constant weight.

The yield of the initial SWCNT/PPTA nanocomposite obtained by the proposed method is 1.072 g (89.33%) at [SWCNT] = 10% by weight.

The characteristics and properties of the obtained nanocomposite material: 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/polypheioxazine according to the proposed method, phenoxazine (FOA) of the structural formula is taken as a monomer

in the amount of 0.1 mol/l (1.2 g) of FAO is dissolved in a mixture of toluene (24 ml) and isopropyl alcohol (16 ml) and 0.12 g of SWCNTs (10% by weight, relative to the mass of the monomer) are added.

The characteristics and properties of the obtained nanocomposite material: 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 0.12 g of MWCNTs are taken (10% by weight, relative to the mass of the monomer).

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 0.12 g of OG is taken (10% by weight, relative to the mass of the monomer).

The characteristics and properties of the obtained nanocomposite material: 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 0.12 g of MWCNTs are taken (10% by weight, relative to the mass of the monomer).

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 0.12 g of OG is taken (10% by weight, relative to the mass of the monomer).

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 0.036 g of SWCNTs are taken (3% by weight, relative to the mass of the monomer).

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 monomer).

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 0.036 g of MWCNTs are taken (3% by weight, relative to the mass of the monomer).

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 0.036 g of SWCNTs are taken (3% by weight, relative to the mass of the monomer).

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 0.036 g of MWCNTs are taken (3% by weight, relative to the mass of the monomer).

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 0.096 g of MWCNTs are taken (8% by weight, relative to the mass of the monomer).

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 0.024 g of OG is taken (2% by weight, relative to the mass of the monomer).

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 14

The method for obtaining a nanocomposite is carried out similarly to example 2, but 0.012 g of SWCNTs are taken (1% by weight, relative to the mass of the monomer).

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 0.06 g of OG is taken (5% by weight, relative to the mass of the monomer).

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, a heat-resistant (thermostable) electrically conductive nanomaterial based on a polyconjugated polymer (PFTA or PFOA) and CNM (RGO, SWCNT or MWCNT) was obtained in an interphase process. The synthesized heterocyclic polyazines - PFTA or PFOA are well adsorbed on the CNM surface due to the stacking effect and functional groups (heteroatoms N and S(O)). The polymer matrix prevents CNM aggregation. The method allows obtaining a nanomaterial with high electrical conductivity up to 5.1 × 10 S/cm - 9.2 × 10 S/cm. According to the prototype, the conductivity of the material does not exceed 6.2 × 10 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/polyaniline 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 its production. 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. Pp. 855-863.

6. Ozkan S.Zh., Karpacheva G.P., Bondarenko G.Y. Phenoxazine polymers: synthesis, structure. // Bulletin of the Academy of Sciences. Chemical Series. 2011. No. 8. P. 1625-1630.

Claims (10)

A method for producing a nanocomposite conductive material based on a polyconjugated polymer and a carbon nanomaterial (CNM), including producing a polyconjugated polymer containing CNM, characterized in that the polyconjugated polymer is a heterocyclic polyazine obtained by interfacial oxidative polymerization of a monomer of the general structural formula where Y in polyazine and in the monomer is a sulfur or oxygen heteroatom, wherein first the monomer is mixed in a solution of a mixture of toluene and isopropyl alcohol, taken in a volume ratio of 1.5:1.0, together with a carbon nanomaterial (CNM), taken in an amount of from 1 to less than 5 wt. %, relative to the mass of the monomer - the organic phase, mixing is carried out in an ultrasonic bath at room temperature until a homogeneous suspension of the organic phase is formed, then an aqueous solution of ammonium persulfate is added to the resulting suspension - the aqueous phase, taken at a ratio of the volumes of the aqueous and organic phases of 1:2, and carry out interphase oxidative polymerization in situ at a temperature of 15°C for at least three hours, the reaction mixture is precipitated twice: first in a 5-fold excess of a mixture of methanol and distilled water, taken in a volume ratio of 1.5:1.0, and then in a two-fold excess of isopropyl alcohol; The resulting product is then filtered, washed with distilled water until the filtrate is colorless, and dried to a constant weight to obtain a nanocomposite conductive material. 2. The method according to paragraph 1, characterized in that an electrically conductive CNM is used, selected from the series: reduced graphene oxide (RGO), single-wall carbon nanotubes (SWCNT), multi-wall carbon nanotubes (MWCNT).