POLYMER COMPOSITION CONTAINING POLYANILINE

Abstract

RENOV24001NL / P0 ABSTRACT The invention relates to a method for preparing a masterbatch comprising a thermoplastic polymer and polyaniline, comprising the following steps of a) Dissolving a thermoplastic polymer in a suitable solvent to obtain a thermoplastic polymer solution; b) Adding aniline to the thermoplastic polymer solution; c) Optionally adding a salt, acid, an oxidizing agent and water to the solution of step b) thereby inducing polymerization of aniline to polyaniline (PANI) to obtain a dissolved blend of thermoplastic polymer and PANI; d) Coagulating the dissolved blend of thermoplastic polymer and PANI to obtain a masterbatch of thermoplastic polymer with PANI. Further the invention relates to a masterbatch of a thermoplastic polymer with a finely divided PANI and the use of the masterbatch in obtaining polymer composites.

Description

RENOV24001NL / P0 -1- POLYMER COMPOSITION CONTAINING POLYANILINE The present invention pertains to a composite antioxidant concentrate composed of thermoplastic polymers, which contain a solution of polyaniline, as well as the methods used for their preparation. Antioxidants are utilized to prevent the degradation of polymers during processing, recycling, and use. Polymer degradation can lead to various negative effects, such as gel formation, changes in viscosity, melt flow index, loss of mechanical and aesthetic properties (e.g. crazing, gloss reduction, chalking), and discoloration. As a result, the number of times that thermoplastics can be recycled is limited, which ultimately reduces the useful lifespan of the polymer or final product. Thermoplastics are particularly susceptible to oxidative degradation during high-temperature melt processing operations and end-use. Generally, polymer degradation results in the formation of free radicals, which can trigger uncontrolled avalanche reactions. Antioxidants are employed to mitigate the formation of free radicals through various mechanisms, such as using complex agents or hydroperoxide decomposers or reducing the number of radicals by using radical scavengers or hydrogen donors. One critical factor that determines the efficiency of an antioxidant is its complete dissolution within the polymer matrix. For an antioxidant to function properly, the oxidation of the polymer chain must occur in close proximity to the antioxidant molecule. This enables the antioxidant molecule to halt the process of thermal-oxidative degradation of polymers. Although existing antioxidants can extend the number of recycling cycles, they often decrease the physical and mechanical properties of thermoplastics. ln one study (See Tsioptsias, C. Textiles, 2, 499510 (2022)), different filaments were produced from pure PP (isotactic PP (Ecolen HZ42Q, Hellenic Petroleum S.A., Thessaloniki, Greece)), and PP-AO (with 4 wt.% of the antioxidant masterbatch (KRITILEN®AO PP9216, Plastika Kritis S.A., Heraklion, Greece)). The results showed that the elastic modulus of filaments decreased from 5069 i 408 MPa for pure PP filaments to 4134 i 449 MPa for PP-AO filaments, the tensile strength of filaments decreased from 549 i 27 MPa for pure PP filaments to 448 i 37 MPa for PP-AO filaments, and the elongation at break of filaments decreased from 34 i 1 % for pure PP filaments to 30 i 1 % for PP-AO filaments. Aniline is a monomer in the polymerization of Polyaniline (PANI). Aniline shows antioxidant properties (See M. GizdavicNikolaidis, CurrentApplied Physics 4, 343 346, (2004)), but quickly oxidizes in air and acquires a red-brown color and is very RENOV24001NL / P0 -2- toxic. Also, its low boiling point (1840 C) does not allow it to be introduced into most thermoplastic polymers using melting extrusion. Polyaniline (PANI) is a conducting polymer and organic semiconductor that belongs to the semi-flexible rod polymer family. The UVVIS results showed that PANl is approximately six times more efficient as a scavenger ofDPPH radicals than aniline, probably because its redox potential is lower (See M. GizdavicNikolaidis, Current Applied Physics 4, 343346, (2004)). PANl was initially discovered as black aniline and can exist in various forms depending on its oxidation level. PANl has doped (emeraldine) and undoped forms. Emeraldine base form (partially oxidized) is environmentally stable, non-toxic, safe for usage and does not undergo any change in chemical structure on prolonged storage. But PANl with doped form is insoluble in any solvent as well, which is attributed to its rigid backbone and lack of melting point (See Radha D. Pyarasani, Journal of Materials Science 54, 974996 (2019). As a result, since polyaniline doesnt melt, it is impossible to melt and dissolve polyaniline in another polymer using extrusion at high temperatures. PANl is easy to detect using Xray diffraction (XRD). Three sharp peaks are observed for PANl (Fig. 1) at different angles of diffraction corresponding to 121, 113 and 322 crystal planes, indicating that the majority of PANl chains are ordered on these three crystal planes (See Sambhu Bhadra, Polymer Testing 27, 851857 (2008)). After polymerization, PANl can be obtained in the form of powder or nanotubes (See Banerjee, S. Nanotechnology 21, 045101 (8pp) (2009)), or it can cover other particles by introducing different particles into the PANl polymerization process (See Beygisangchin, M. Polymers 2021, 13, 2003 (2021)). These methods, along with others, can improve the even distribution of PANl in various polymer matrices, including thermoplastic polymers. However, the antioxidant properties of a blend of a thermoplastic polymer and PANl are still insufficient, which limits the possibilities of recycling the thermoplastic polymers. The present invention aims to improve the recyclability of thermoplastic polymers with the use of PANl as an antioxidant polymer. Summary of the invention The invention relates to method for preparing a masterbatch comprising a thermoplastic polymer and polyaniline, comprising the following steps a) Dissolving a thermoplastic polymer in a suitable solvent to obtain a thermoplastic polymer solution; RENOV24001NL / P0 -3- b) Adding aniline to the thermoplastic polymer solution; c) Optionally adding a salt, acid, oxidizing agent and water to the solution of step b) thereby inducing polymerization of aniline to polyaniline (PANI) to obtain a dissolved blend of thermoplastic polymer and PANl; d) Coagulating the dissolved blend of thermoplastic polymer and PANl to obtain a masterbatch of thermoplastic polymer with PANl. The invention further relates to a masterbatch comprising a highly dispersed PANl, which has excellent antioxidant properties and can be blended into thermoplastic polymers or recycled thermoplastic polymers and prevents polymer degradation in subsequent recycling processes. The invention further relates to a composite material comprising a thermoplastic polymer, or recycled thermoplastic material and the masterbatch of the invention. Advantages of the present invention are the provision of an improved method to preparing highly dispersed PANl in a thermoplastic matrix which shows improved properties, especially preventing or slowing down of degradation due to subsequent extrusion steps and improving recyclability of thermoplastic polymers without deterioration of important rheological properties and mechanical properties such as tensile strength, Young's modulus, flexural strength, flexural modulus and impact strength. Detailed description of the invention The invention relates to a method for preparing a masterbatch comprising a thermoplastic polymer and polyaniline, comprising the following steps a) Dissolving a thermoplastic polymer in a suitable solvent to obtain a thermoplastic polymer solution; b) Adding aniline to the thermoplastic polymer solution; c) Optionally adding a salt, acid, oxidizing agent and water to the solution of step b) thereby inducing polymerization of aniline to polyaniline (PANI) to obtain a dissolved blend of thermoplastic polymer and PANl; d) Coagulating the dissolved blend of thermoplastic polymer and PANl to obtain a masterbatch of thermoplastic polymer with PANl. The thermoplastic polymer to be dissolved in step a) of the process of the invention can be a wide variety of thermoplastic polymers. The thermoplastic polymer may be a mixture of polymers. Preferably the thermoplastic polymer is selected from polyamide, acrylonitrile butadiene styrene, polyethylene terephthalate and polylactide. More preferably the thermoplastic polymer is a polyamide. RENOV24001NL / P0 -4- Examples of preferred polyamides are polyamide 6, polyamide 6-6, polyamide 4-6, polyamide 6-10, alcohol-soluble polyamide resin, polyamide 11, polyamide 12, polyamide 6- 12, polyamide 6-9, polyamide 6-10, polyamide 12-12 and polyphthalamide. ln step a) the thermoplastic polymer is dissolved in a suitable solvent. Examples of suitable solvents are N-Methyl-2-pyrrolidone, xylenes, dimethyl sulfoxide, dimethyl formamide, dimethyl acetamide, diethyl ether, isopropyl alcohol, butyl alcohol, acetonitrile, ethylene dichloride, ethyl acetate, ethylene glycol, formic acid, tetrahydrofuran, esters, ethanol, acetone, dioxane, chloroform, phenol, toluene, nitrobenzene, dichloromethane, benzoyl chloride, benzene, pyridine, butyl acetate, nitrobenzene, hexane, acetonitrile, acetic acid, methanol, water or mixtures thereof. ln practice each thermoplastic polymer has a number of solvents that may be preferably used. Preferred combinations of thermoplastic polymers and solvents are chosen from the combinations: polyamide (PA) with the solvent formic acid, and a solution of CaClz or LiCl in ethanol or methanol; acrylonitrile butadiene styrene (ABS) with a solvent chosen from esters, ketones (such as acetone), chloroform, ethylene dichloride; polyethylene terephthalate (PET) with a solvent chosen from phenol, trifluoroacetic acid, o-chlorophenol, tetrachlorethane, nitrobenzene; polylactide (PLA) with a solvent chosen from dioxane, acetonitrile, chloroform, methylene chloride, 1,1,2-trichloroethane, dichloroacetic acid. The concentration of the thermoplastic polymer in organic solvent in step a) can vary from 0.1 wt% to 30 wt% (depending on the polymer, solvent, and dissolution temperature). The preferred concentration of the thermoplastic polymer in organic solvent in step a) is between 5wt% and 20 wt%. ln step b) aniline is added to the polymer solution. The amount of aniline preferably ranges between 0.5 wt% and 50 wt% relative to the amount of thermoplastic polymer. Preferably an organic solvent is used to add aniline in step b). Adding a small amount of water with the aniline is also permissible, provided that the thermoplastic polymer remains in solution. The mixture is stirred until it is fully mixed. After fully mixing, in step c) a solution of an oxidizing agent is added to the mixture to polymerize the aniline. Suitable oxidizing agents include oxidizing salts, like for example sodium and potassium chlorate, potassium permanganate, potassium dichromate, or ammonium persulfate, and peroxides like for example hydrogen peroxide or dibenzoyl peroxide. The polymerization reaction should be stirred constantly and cooled. The addition of oxidizing salts (preferably one of sodium and potassium chlorate, potassium dichromate, potassium permanganate or ammonium persulfate) facilitate the polymerization of aniline to polyaniline. RENOV24001NL / P0 -5- The amount of oxidizing salt ranges preferably between 0.1 wt% and 30 wt%, more preferably between 1-15 wt%, more preferably between 2-8 wt% relative to the weight of the thermoplastic polymer solution. Hydrogen peroxide and dibenzoyl peroxide, as an oxidant, can accelerate the synthesis processes and affects the structure of PANI, but the synthesis of PANl can be carried out both with and without hydrogen peroxide or dibenzoyl peroxide. Preferably the amount of dibenzoyl peroxide or hydrogen peroxide ranges between 0 wt% and 15 wt%, preferably between 1-10 wt%, more preferably between 1-5 wt% relative to the weight of the thermoplastic polymer solution. ln step c) a further salt can be present during the polymerization of aniline to PANI. The further salt is preferably selected from sodium chloride, potassium chloride, calcium chloride, copper sulfate, ferrous sulfate, lithium chloride, magnesium sulfate, potassium iodide, sodium acetate, calcium acetate or mixtures thereof. Preferably the further salt is selected from lithium chloride, calcium chloride, ferrous sulfate, potassium iodide or mixtures thereof. The amount of further salt ranges preferably between 0 wt% and 30 wt%, more preferably between 1-15 wt%, more preferably between 2-8wt% relative to the weight of the thermoplastic polymer solution. ln step c) an acid can be present during the polymerization of aniline to PANI. The acid is preferably selected from acetic acid, hydrochloric acid, sulfuric acid, nitric acid, dichloroacetic acid, formic acid, hydrofluoric acid, phosphoric acid, citric acid, carbonic acid or mixtures thereof. In a preferred embodiment the acid is selected from sulfuric acid, formic acid, hydrochloric acid, acetic acid, citric acid or mixtures thereof. Preferably the amount of acid ranges between 0 wt% and 25 wt%, preferably between 1-19 wt%, more preferably between 8-15 wt% relative to the weight of the thermoplastic polymer solution. The temperature during polymerization of aniline is preferably maintained lower than: (1) crystallization temperature of the thermoplastic polymer; (2) boiling temperature of the polymer solvent. Preferably the temperature of polymerization ranges between 15 °C and 120 °C, preferably the temperature of polymerization ranges between 20 °C and 80 °C, more, preferably the temperature of polymerization ranges between 25 °C and 50 °C. RENOV24001NL / P0 -6- ln step c) a polyaniline (PANI) is being formed. PANl can be prepared in different forms, like for example in the form of leucomeraldine, emeraldine or pernigraniline. Preferably the PANl formed in step c) is in the form of (protonated) emeraldine. After polymerization, the mixture needs to be coagulated to obtain a solid composite mixture. The liquid solution of thermoplastic polymer can be coagulated when a non-solvent (coagulant) is added to the solution at a concentration exceeding the critical concentration at which the thermoplastic transitions from a liquid dissolved state to a solid state. Below the critical concentration, the non-solvent is unable to coagulate the liquid thermoplastic solution. Preferred combinations of solvents and coagulants depend on the used thermoplastics: For polyamide (PA) the preferred solvents are: formic acid, or a solution CaClz or LiCl in ethanol or methanol; the preferred coagulants for these solutions are: acetone, DMF, NMP, water, dioxane. For acrylonitrile butadiene styrene (ABS) the preferred solvents are: esters, ketones (such as acetone), chloroform, ethylene dichloride; the preferred coagulant for these solutions is water. For polyethylene terephthalate (PET) the preferred solvents are: phenol, o-chlorophenol, tetrachlorethane, nitrobenzene, trifluoroacetic acid and nitrobenzene; the preferred coagulants for these solutions are: diethyl ether, water, ethanol, methanol, acetone, dioxane, toluene. For polylactide (PLA) the preferred solvents are: dioxane, acetonitrile, chloroform, methylene chloride, 1,1,2-trichloroethane, dichloroacetic acid; the preferred coagulants for these solutions are: ethanol, methanol, water, isopropanol. Preferably Water is used as a coagulant. It is preferred to add water in an amount twice that of the initial organic solvent (as used in step a), preferably to add water in an amount 1.5 times greater than the amount of the initial organic solvent (as used in step a), more preferably to add water in the same amount as the initial organic solvent (as used in step a). Filtration and washing of the solid composite need to be carried out until all residues from the polymerization reaction have been removed. Water or organic solvents can be used as washing solutions. The solid composite is preferably to dry for removal residual solvents after the washing process. The final composite is a fine powder that consists of polyaniline polymer nanoparticles finely dispersed in the thermoplastic polymer. The invention also relates to a masterbatch. The masterbatch comprises a thermoplastic polymer and a polyaniline (PANI), wherein the PANl is present as a dispersed phase in a RENOV24001NL / P0 -7- form of particles with the size range between 1 nm and 250 nm. Preferable at least70% of the particles of PANl have a size range between 3 nm and 150 nm. The particle size of PANl can be determined with Transmission electron microscopy (TEM) (see for example 1: Figure 5, 6 and 7). The thermoplastic polymer in the masterbatch is a preferably chosen from a polyamide, polystyrene acrylonitrile butadiene styrene, polyethylene terephthalate and polylactide. Preferably the masterbatch contains a polyamide, which is preferably selected from polyamide 6, polyamide 6-6, polyamide 4-6, polyamide 6-10, alcohol-soluble polyamide resin, polyamide 11, polyamide 12, polyamide 6-12, polyamide 6-9, polyamide 6-10, polyamide 12-12 and polyphthalamide. The amount of PANl in the masterbatch typically ranges between 1 and 25 wt%, preferably the amount of PANl ranges between 3 and 15 wt%, more preferably the amount of PANl ranges between 4 and 8 wt%, relative to the weight of the masterbatch. The invention further relates to a thermoplastic composite comprising a polymer selected from polyethylene terephthalate, thermoplastic polyurethane, polypropylene, polyethylene, polystyrene, acrylonitrile butadiene styrene, polyvinyl chloride, polylactide, polyphenylene sulfide, polyphthalamide, polybutylene terephthalate, polyimide, polyether ether ketone, polytetrafluoroethylene , polyetherimide, polyvinyl alcohol and polyamide and the masterbatch as obtained in the method as defined above or as described above. The concentration of PANl in the thermoplastic composite ranges between 0.0001 and 0.4 wt%, preferably the concentration of PANl ranges between 0.001 and 0.3 wt%, more preferably the concentration of PANl ranges between 0.01 and 0.15 wt%. Preferably the PANl is present as a dispersed phase in a form of particles with the size range between 1 and 250 nm. Preferable at least 70% of the particles of PANl have a size range between 3 nm and 150 nm. The particle size can be determined with TEM. The thermoplastic composite according to the invention has the advantage that it is very stable and can be recycled many times (for example up to 8 times) with minor loss of its physical properties. The thermoplastic composite can be prepared by methods known to the skilled man. For example the thermoplastic composite is prepared by coextrusion of a polymer selected from polyethylene terephthalate, thermoplastic polyurethane, polypropylene, polyethylene, polystyrene, acrylonitrile butadiene styrene, polyvinyl chloride, polylactide, polyphenylene sulfide, polyphthalamide, polybutylene terephthalate, polyimide, polyether ether ketone, polytetrafluoroethylene , polyetherimide, polyvinyl alcohol and polyamide; with the masterbatch as defined above. RENOV24001NL / P0 -8- @@ Fig.1. Powder Xray Diffraction (XRD) spectra plot of PANI, the numbers around the peaks indicate hkl values or crystal planes corresponding to the peaks. The y-axis represents intensity, while the x-axis represents 20 (Degree). Fig 2. Size distribution of the granules in the masterbatch powder of example 1. The y-axis represents volume density (%), while the x-axis represents size classes (um). Fig 3. Raman spectrum for masterbatch solution of PANl in polyamide copolymer with the running averaged of 10 points. The y-axis represents Raman intensity, while the x-axis represents wavenumber (cm'1). Fig.4. Powder X-ray Diffraction (XRD) spectra of the thermoplastic matrix of a polyamide copolymer and a masterbatch consisting of polyaniline in this thermoplastic matrix. The y- axis represents intensity, while the x-axis represents 20 (Degree). The black dashed line represents the spectrum of the thermoplastic matrix, while the black solid line on the graph represents the spectrum of the masterbatch consisting of polyaniline in this thermoplastic matrix. Fig.5. Transmission Electron Microscopy (TEM) images of the masterbatch sample showing a polyaniline nanoparticle with an average size of 30 nm in a polyamide copolymer matrix. Fig.6. Transmission Electron Microscopy (TEM) images of the masterbatch sample showing polyaniline nanoparticles in a polyamide copolymer matrix. Fig.7. Transmission Electron Microscopy (TEM) images of the masterbatch sample showing polyaniline nanoparticles in a polyamide copolymer matrix. Fig.8. Rotational viscosity. The y-axis represents viscosity values in units of Pa-s, while the x- axis represents shear rate values in units of 1 / s. Circles in the graph indicate rotational viscosity values for the compound with the masterbatch from Example 1, and triangles in the graph indicate rotational viscosity values for the compound without the masterbatch from Example 1. Fig.9. Rotational viscosity. The y-axis represents viscosity values in units of Pa-s, while the x- axis represents shear rate values in units of 1 / s. Circles in the graph indicate rotational viscosity values for the compound with the masterbatch from Example 8, and triangles in the graph indicate rotational viscosity values for the compound without the masterbatch from Example 8. Examples Example 1. In this example, 190 grams of polyamide copolymerwas dissolved in a solution of 850 milliliters of ethanol and 100 milliliters of water at a temperature of65 0C. After RENOV24001NL / P0 -9- complete dissolution of polyamide copolymer, a solution of 21 milliliters of aniline in 140 milliliters of ethanol and 10 milliliters ofwaterwas added to the solution with polyamide copolymer with constant stirring during 10 minutes. Then a solution of 500 milliliters of 1,57 M HCL, 10 grams of LiCl and 53 grams of potassium dichromate was pre-prepared and added to the solution of polyamide copolymer and aniline, and the resulting mixture was intensive stirred with cooling. As a result, polymerization of aniline to polyaniline occurs in a solution of polyamide copolymer. Intensive stirring and cooling occurred during the entire process of aniline polymerization until itwas completed within 8 hours. Then the resulting solution was slowly added to 2 L ofwater with intensive stirring over a period of 2 h for coagulation of the blend of polyamide copolymer and PANl from solution to obtain a masterbatch. The resulting solid particles of the masterbatch of PA and PANl were thoroughly washed after completion of the coagulation process and filtered with thorough washing with water and acetone. After completely washing process, the obtained masterbatch was allowed to dry 30 min, 80 °C in dry oven and milled in disc mill to obtain a composite in the form of a fine powder. The size distribution of the granules in the powderwas obtained in aqueous dispersion, D10 of this powder is 20 um, D50 of this powder is 160 um, D90 of this powder is 296 um (Fig.2). The uniform distribution of PANl throughout the masterbatch can be revealed using Raman (Fig.3). The x-axis represents the wavenumber (cm1), and the y-axis represents the Raman intensity. The spectrum contains the most markers for PANl bands, located at 1604 and 1592 cm'1, corresponding to carbon-carbon single and double band stretching vibrations in benzene and quinine type rings, respectively. There are specific bands of C-N stretches of amine sites at 1220 cm'1. The stretching vibrations of an intermediate bond C-N are seen in Raman spectra with characteristic frequency around 1330 cm'1 (See Hasoon Salah Abdullah, International Journal of Physical Sciences, 7(38), 5468-5476, (2012)). The diffraction patterns of the obtained masterbatch were measured using an X'TRA powder diffractometer (Thermo, Switzerland) with a vertical 9 / 9 geometry goniometer, Bragg- Brentano focusing, and a linear semiconductor detector. The masterbatch was in a powder form. The radiation source was an Xray tube with a copper anode, with an average wavelength ofCuKd = 0.15418 nm. The generator currentwas 40 mA, and the voltage was 35 W. The crystallite size, calculated using the Scherrer formula, was approximately 100 nm for the peak at 20 degrees, 7 nm for the reflex at 24 degrees, and around 5 nm for the peaks at 38 and 41 degrees (Fig.4). According to the diffraction data, the masterbatch had two phases and consisted of crystalline polyaniline and amorphous polyamide copolymer. RENOV24001NL / P0 -10- The particle size of polyaniline, ranging from 5 to 100 nm with an average size of 30 nm, was confirmed byTEM images (Fig.5, Fig.6, Fig.7). Example 2. In this example, post-industrial carpet polyamide-6 waste was used as the primary thermoplastic. The material consisted of20mm chopped polyamide-6 filaments made from post-industrial carpet waste. First, before extrusion, both samples were dried in a drying oven at a temperature of 80 °C for 16 hours: 10 kg of polyamide-6 fibers and 100 grams of masterbatch from Example 1. The second step was the compounding of the obtained compacted material and the masterbatch from Example 1. The twin screw extruder's temperature profile was as follows: 240 oC 240 oC - 250°C 250 oC 260 oC 260 oC 260 oC 260 oC 260 °C. The screw rotation speed was 250 rpm. The amount of polyamide-6 fibers was 10 kg, and the amount of the additive from Example 1 was 100 grams. Both materials were fed through the main feeder of the extruder. Thus, the final thermoplastic composite compound was obtained. The rotational rheology analysis of this compound was conducted in full accordance with the ISO 6721-10 (2015) standard at 260 °C (Figure 8, black circles). For comparison, the measured values of rotational viscosity for the material derived from post-industrial carpet polyamide-6 waste at the same temperature after processing on a twin-screw extruder under similar temperatures conditions and screw speed, but without the use of the masterbatch from Example 1, are also plotted on the graph (Fig.8, black triangles). In the share rate range of 1 to 100 1 / s (Fig.8), the rotational viscosity of the compound with the masterbatch from Example 1 is, on average, 2 times higher than the viscosity of the compound without the masterbatch from Example 1. For measuring mechanical properties, test specimens (ISO 20753) were produced using injection molding out of this compound, the compound was obtained using the method described above. The temperature regime for injection molding was as follows: 260-260-250- 240°C. For measuring tensile strength and Young's modulus, ten standard test specimens were produced. After measuring the tensile strength and Young's modulus, the test specimens were crushed into fine shavings and then remolded using the injection molding machine under the same molding conditions. This operation was repeated 4 times. The data for tensile strength and Young's modulus are presented in Table 1 below. Table 1 shows the average values averaged over 10 measurements. RENOV24001NL / P0 -11- Table 1. Mechanical strength of injection molding samples for compounds after recycling. Number of cycle of Tensile Young's modulus, _-_ Example 3. In this example, virgin polyethylene terephthalate was used as the primary thermoplastic. The material consists of standard 3mm polyethylene terephthalate pellets. First, before extrusion, both samples were dried in a drying oven at a temperature of 110°C for 8 hours: 15 kg of polyethylene terephthalate pellets and 300 grams of masterbatch from Example 1. The second step was the compounding of the polyethylene terephthalate pellets and the masterbatch from Example 1. The twin screw extruder's temperature profile was as follows: 270 °C 275 °C - 280°C 285 °C 285 °C 285 °C 285 °C 285 °C 285 °C. The screw rotation speed was 300 rpm. The amount of polyethylene terephthalate was 15 kg, and the amount of the additive from Example 1 was 300 grams. Both materials were fed through the main feeder of the extruder. Thus, the final thermoplastic composite compound was obtained. Rotational viscosity was measured at 285°C. In the share rate range of 1 to 500 1 / s, the viscosity of the compound with the masterbatch from Example 1 is, on average, 4 times higher than the viscosity of the compound without the masterbatch from Example 1. Standard injection molding test specimens for measuring strength properties were also molded from this compound, obtained using the method described above. The temperature regime for injection molding was as follows: 285-285-280-275°C. For measuring tensile strength and Young's modulus, ten standard test specimens were produced. After measuring the tensile strength and Young's modulus, test specimens were crushed into fine shavings and then remolded using the injection molding machine under the same molding conditions. This operation was repeated 3 times. The data for tensile strength and Young's modulus are presented in Table 2 below. Table 2 shows the average values averaged over 10 measurements. RENOV24001NL / P0 -12- Table 2. Mechanical strength of injection molding samples for compounds after recycling. Number of cycle of Tensile Young's modulus, _-_ Example 4. In this example, virgin polylactide was used as the primary thermoplastic. The material consists of standard 3mm polylactide pellets. First, before extrusion, both samples were dried in a drying oven at a temperature of60°C for 10 hours: 19 kg of polylactide pellets and 247 grams of masterbatch from Example 1. The second step was the compounding of the polylactide pellets and the masterbatch from Example 1. The twin screw extruder's temperature profile was as follows: 175 °C 175 °C - 180°C 180 °C 190 °C 190 °C 200 °C 200°C 200 °C. The screw rotation speed was 175 rpm. The amount of polylactide was 19 kg, and the amount of the additive from Example 1 was 247 grams. Both materials were fed through the main feeder of the extruder. Thus, the final thermoplastic composite compound was obtained. Rotational viscosity was measured at 200°C. In the share rate range of 1 to 150 1 / s, the viscosity ofthe compound with the masterbatch from Example 1 is, on average, 1.7 times higher than the viscosity of the compound without the masterbatch from Example 1. Standard injection molding test specimens for measuring strength properties were also molded from this compound, obtained using the method described above. The temperature regime for injection molding was as follows: 200-200-190-185°C. For measuring tensile strength and Young's modulus, ten standard test specimens were produced. After measuring the tensile strength and Young's modulus, the test specimens were crushed into fine shavings and then remolded using the injection molding machine under the same molding conditions. This operation was repeated 1 time. The data for tensile strength and Young's modulus are presented in Table 3 below. Table 3 shows the average values averaged over 10 measurements. RENOV24001NL / P0 -13- Table 3. Mechanical strength of injection molding samples for compounds after recycling. Number of cycle of Tensile Young's modulus, _-_ Example 5. In this example, virgin thermoplastic polyurethane was used as the primary thermoplastic. The material consists of standard 3.5 mm thermoplastic polyurethane pellets. First, before extrusion, both samples were dried in a drying oven at a temperature of 55°C for 19 hours: 11 kg of thermoplastic polyurethane pellets and 90 grams of PA masterbatch from Example 1. The second step was the compounding of the thermoplastic polyurethane pellets and the PA masterbatch from Example 1. The twin screw extruder's temperature profile was as follows: 185 °C 190 °C -190°C 200 oC 210 °C 210 °C 210 °C 210 °C 210 °C. The screw rotation speed was 190 rpm. The amount of thermoplastic polyurethane pellets was 11 kg, and the amount of the additive from Example 1 was 90 grams. Both materials were fed through the main feeder of the extruder. Thus, the final thermoplastic composite compound was obtained. Rotational viscositywas measured at 210°C. In the share rate range of 1 to 300 1 / s, the viscosity of the compound with the masterbatch from Example 1 is, on average, 3 times higher than the viscosity of the compound without the masterbatch from Example 1. Standard injection molding test specimens for measuring strength properties were also molded from this compound, obtained using the method described above. The temperature regime for injection molding was as follows: 210-200-190-180°C. For measuring tensile strength, ten standard test specimens were produced. After measuring the tensile strength, the test specimens were crushed into fine shavings and then remolded using the injection molding machine under the same molding conditions. This operation was repeated 3 times. The data for tensile strength are presented in Table 4 below. Table 4 shows the average values averaged over 10 measurements. RENOV24001NL / P0 -14- Table 4. Mechanical strength of injection molding samples for compounds after recycling. Number of cycle of Tensile _- Example 6. In this example, virgin polyethylene was used as the primary thermoplastic. The material consists of standard 2.3 mm thermoplastic polyethylene pellets. First, before extrusion, both samples were dried in a drying oven at a temperature of 55°C for 1 hours: 31 kg of polyethylene pellets and 150 grams of masterbatch from Example 1. The second step was the compounding of the polyethylene pellets and the masterbatch from Example 1. The twin screw extruder's temperature profile was as follows: 185 °C 190 °C - 195°C 200 °C 200 °C 200 °C 200 °C 200 °C 200 °C. The screw rotation speed was 183 rpm. The amount of polyethylene pellets was 31 kg, and the amount of the additive from Example 1 was 950 grams. Both materials were fed through the main feeder of the extruder. Thus, the final thermoplastic composite compound was obtained. Rotational viscosity was measured at 210°C. In the share rate range of 1 to 1000 1 / s, the viscosity of the compound with the masterbatch from Example 1 is, on average, 1.2 times higher than the viscosity of the compound without the masterbatch from Example 1. Standard injection molding test specimens for measuring strength properties were also molded from this compound, obtained using the method described above. The temperature regime for injection molding was as follows: 200-200-190-190°C. For measuring tensile strength, ten standard test specimens were produced. After measuring the tensile strength, the test specimens were crushed into fine shavings and then remolded using the injection molding machine under the same molding conditions. This operation was repeated 2 times. The data for tensile strength are presented in Table 5 below. Table 5 shows the average values averaged over 10 measurements. RENOV24001NL / P0 -15- Table 5. Mechanical strength of injection molding samples for compounds after recycling. Number of cycle of Tensile Young's _- Example 6. In this example, 50 grams of polyethylene terephthalate was dissolved in a solution of 1000 milliliters of tetrachlorethane / phenol with a mass ratio of 9:1 at a temperature of 70 °C with stirring. After complete dissolution of polyethylene terephthalate, a solution of 5 milliliters of aniline was added to the mixture with polyethylene terephthalate with stirring during 15 minutes. Then a solution of 1 gram of ammonium persulfate in 5 grams ofwater and 70 grams of phenol was pre-prepared and added to the solution of polyethylene terephthalate and aniline, and the resulting mixture was intensively stirring with cooling. As a result, polymerization of aniline to polyaniline occurs in a solution of polyethylene terephthalate. Intensive stirring and cooling occurred during the entire process of aniline polymerization until itwas completed within 12 hours. The resulting solution was slowly added to 1 L of ethanol with intensive stirring over a period of 20 min to allow the PET-masterbatch to coagulate from solution. The resulting solid particles of the PET-masterbatch were thoroughly washed after completion of the coagulation process and filtered with thorough washing with water and ethanol. After completing the washing process, the obtained PET masterbatch was allowed to dry for 2 h at 70°C in a dry oven and milled in a disc mill to obtain a PET masterbatch in the form of a fine powder. The size distribution of the granules in the powder is as follows: D10 of this powder is 10 um, D50 of this powder is 140 um, D90 of this powder is 260 um. Diffraction and TEM measurements were carried out on the same equipment and under the same conditions as in Example 1, and according these data the particle size of polyaniline in PET the masterbatch is ranging from 10 to 123 nm with an average size of 38 nm. Example 7. In this example, post-industrial fishnets polyethylene terephthalate waste was used as the primary thermoplastic. The material consisted of 10mm chopped polyethylene RENOV24001NL / P0 -16- terephthalate filaments made from post-industrial fishnets waste. First, before extrusion, both samples were dried in a drying oven at a temperature of 120°C for 16 hours: 23 kg of polyethylene terephthalate fibers and 480 grams of PET masterbatch from Example 6. The second step was the compounding of the obtained polyethylene terephthalate material and the PET masterbatch from Example 6. The twin screw extruder's temperature profile was as follows: 273°C 276°C - 280°C 285°C 290°C 290°C 290°C 290°C 290°C. The screw rotation speed was 320 rpm. The amount of polyethylene terephthalate fibers was 23 kg, and the amount of the PET masterbatch from Example 6 was 480 grams. Both materials were fed through the main feeder of the extruder. Thus, the final thermoplastic composite compound was obtained. Rotational viscositywas measured at 285°C. In the share rate range of 1 to 300 1 / s, the viscosity of the compound with the masterbatch from Example 6 is, on average, 3.5 times higher than the viscosity of the compound without the masterbatch from Example 6. Standard injection molding test specimens for measuring strength properties were also molded from this compound, obtained using the method described above. The temperature regime for injection molding was as follows: 285°C 285°C280°C275°C. For measuring tensile strength and Young's modulus, ten standard test specimens were produced. After measuring the tensile strength and Young's modulus, the test specimens were crushed into fine shavings and then remolded using the injection molding machine under the same molding conditions. This operation was repeated 2 times. The data for tensile strength and Young's modulus are presented in Table 6 below. Table 6 shows the average values averaged over 10 measurements. Table 6. Mechanical strength of injection molding samples for compounds after recycling. Number of cycle of Tensile Young's modulus, _-_ RENOV24001NL / P0 -17- Example 8. In this example, 150 grams of polyamide-6 was dissolved in a solution of 950 milliliters of methanol, 30 milliliters ofwater and 100 grams of CaClz at a temperature of 50 °C with stirring. After complete dissolution of polyamide-6, a solution of 17 milliliters of aniline in 100 milliliters of methanol and 5 milliliters of waterwas added to the solution with polyamide-6 with stirring during 30 minutes. Then a solution of 10 grams of copper sulfate and 30 grams of potassium permanganate was dissolved of200 milliliters of methanol and 50 milliliters of water, and added to the solution of polyamide-6 and aniline, and the resulting mixture was intensive stirred with cooling. As a result, polymerization of aniline to polyaniline occurs in a solution of polyamide-6. Intensive stirring and cooling occurred during the entire process of aniline polymerization until itwas completed within 4 hours. Then the resulting solution was slowly added to 2 L of dioxane and 0,5 L ofwater with intensive stirring over a period of 1 h for coagulation of the PA6 masterbatch from solution. The resulting solid particles of the PA6 masterbatch were thoroughly washed after completion of the coagulation process and filtered with thorough washing with water and dioxane. After completing the washing process, the obtained PA6 masterbatch was allowed to dry for 50 min at 70 °C in a drying oven and milled in a disc mill to obtain a PA6 masterbatch in the form of a fine powder. The size distribution of the granules in the powderwas obtained in aqueous dispersion, D10 of this powder is 30 um, D50 of this powder is 180 um, D90 of this powder is 320 um. Diffraction and TEM measurements were carried out on the same equipment and under the same conditions as in Example 1, and according these data the particle size of polyaniline in the masterbatch is ranging from 3 to 70 nm with an average size of 21 nm. Example 9. In this example, virgin polyamide-6 was used as the primary thermoplastic. The material consists of standard 2.7mm thermoplastic polyamide-6 pellets. First, before extrusion, both samples were dried in a drying oven at a temperature of 78°C for 14 hours: 9 kg of polyamide-6 pellets and 270 grams of masterbatch from Example 8. The second step was the compounding of the polyamide-6 pellets and the masterbatch from Example 8. The twin screw extruder's temperature profile was as follows: 250°C250°260°C265°C270°C270°C270°C 270°C270°C. The screw rotation speed was 230 rpm. The amount of polyamide-6 fibers was 9 kg, and the amount of the additive from Example 8 was 270 grams. Both materials were fed through the main feeder of the extruder. Thus, the final thermoplastic composite compound was obtained. The rotational rheology analysis of this compound was conducted in full accordance with the ISO 6721-10 (2015) standard at 260 °C (Figure 9, round black circles). For comparison, the measured values of rotational viscosity for the material derived from virgin polyamide-6 at RENOV24001NL / P0 -18- the same temperature after processing on a twin-screw extruder under similar temperatures conditions and screw speed, but without the use of the masterbatch from Example 8, are also plotted on the graph (Fig.9, triangular black dots). In the share rate range of 1 to 100 1 / s (Fig.9), the rotational viscosity of the compound with the masterbatch from Example 8 is, on average, 1.6 times higher than the viscosity of the compound without the masterbatch from Example 8. Standard injection molding test specimens for measuring strength properties were also molded from this compound, obtained using the method described above. The temperature regime for injection molding was as follows: 260°C 260°C 250°C 240°C. For measuring tensile strength and Young's modulus, ten standard test specimens were produced. After measuring the tensile strength and Young's modulus, the test specimens were crushed into fine shavings and then remolded using the injection molding machine under the same molding conditions. This operation was repeated 8 times. The data for tensile strength and Young's modulus are presented in Table 7 below. Table 7 shows the average values averaged over 10 measurements. Table 7. Mechanical strength of injection molding samples for compounds after recycling. Number of cycle of Tensile Young's modulus, recycling strength, MPa MPa _-_ ___ ___ RENOV24001NL / P0 -19- Example 10. In this example, 60 grams of acrylonitrile butadiene styrene was dissolved in a solution of 900 milliliters of acetone and 100 milliliters ofwater at a temperature of 40 °C while stirring. After complete dissolution ofABS, a solution of 180 milliliters of aniline in 200 milliliters of acetone and 50 milliliters ofwaterwas added to the solution with acrylonitrile butadiene styrene with stirring during 7 minutes. Then a solution of 200 milliliters of 2,1 M HCL and 80 grams of hydrogen peroxide was added to the solution ofABS and aniline, and the resulting mixture was intensive stirred with cooling. As a result, polymerization of aniline to polyaniline occurred in a solution of acrylonitrile butadiene styrene. Intensive stirring and cooling occurred during the entire process of aniline polymerization until itwas completed within 3 hours. The resulting solution was slowly added to 4 L ofwater with intensive stirring over a period of 4.5 h for the coagulation of theABS masterbatch from solution. The resulting solid particles of theABS masterbatch were thoroughly washed after completion of the coagulation process and filtered with thorough washing with water. After completing the washing process, the obtainedABS masterbatch was dried for 13 min at 65 °C in a drying oven and milled in a disc mill to obtain anABS masterbatch in the form of a fine powder. The size distribution of the granules in the powderwas obtained in aqueous dispersion, D10 of this powder is 18 um, D50 of this powder is 149 um, D90 of this powder is 250 um. Diffraction and TEM measurements were carried out on the same equipment and under the same conditions as in Example 1, and according these data the particle size of polyaniline in the masterbatch is ranging from 30 to 149 nm with an average size of 52 nm. Example 11. In this example, virgin acrylonitrile butadiene styrene was used as the primary thermoplastic. The material consists of standard 3mm thermoplastic acrylonitrile butadiene styrene pellets. First, before extrusion, both samples were dried in a drying oven at a temperature of80°C for 10 hours: 29 kg of acrylonitrile butadiene styrene pellets and 70 grams of masterbatch from Example 10. The second step was the compounding of the acrylonitrile butadiene styrene pellets and the masterbatch from Example 10. The twin screw extruder's temperature profile was as follows: 240°C245°C250°C255°C255°C255°C255°C255°C255 °C. The screw rotation speed was 410 rpm. The amount of acrylonitrile butadiene styrene pellets was 29 kg, and the amount of the additive from Example 10 was 70 grams. Both materials were fed through the main feeder of the extruder. Thus, the final thermoplastic composite compound was obtained. Rotational viscositywas measured at 250°C. In the share rate range of 1 to 200 1 / s, the viscosity of the compound with the masterbatch from Example 10 is, on average, 1.4 times RENOV24001NL / P0 -20- higher than the viscosity of the compound without the masterbatch from Example 10. Standard injection molding test specimens for measuring strength properties were also molded from this compound, obtained using the method described above. The temperature regime for injection molding was as follows: 255°C 255°C 250°C 245°C. For measuring tensile strength and Young's modulus, ten standard test specimens were produced. After measuring the tensile strength and Young's modulus, the test specimens were crushed into fine shavings and then remolded using the injection molding machine under the same molding conditions. This operation was repeated 1 time. The data for tensile strength and Young's modulus are presented in Table 8 below. Table 8 shows the average values averaged over 10 measurements. Table 8. Mechanical strength of injection molding samples for compounds after recycling. Number of cycle of Tensile Young's modulus, recycling strength, MPa MPa RENOV24001NL / P0 -21- EMBODIMENTS 1) A method for preparing a masterbatch comprising a thermoplastic polymer and polyaniline, comprising the following steps a) Dissolving a thermoplastic polymer in a suitable solvent to obtain a thermoplastic polymer solution; b) Adding aniline to the thermoplastic polymer solution; c) Optionally adding a salt, acid, an oxidizing agent and water to the solution of step b) thereby inducing polymerization of aniline to polyaniline (PANI) to obtain a dissolved blend of thermoplastic polymer and PANI; d) Coagulating the dissolved blend of thermoplastic polymer and PANI to obtain a masterbatch of thermoplastic polymer with PANI. 2) The method according to claim 1 wherein the oxidizing agent is an oxidizing salt and the oxidizing salt is selected from sodium and potassium chlorate, potassium permanganate, potassium dichromate, or ammonium persulfate. 3) The method according to any one of the preceding claims, wherein the amount of oxidizing salt ranges preferably between 0.1 wt% and 30 wt%, more preferably between 1-15 wt%, more preferably between 2-8wt% relative to the weight of the thermoplastic polymer solution. 4) The method according to any one of the preceding claims, wherein as oxidizing agents dibenzoyl peroxide and / or hydrogen peroxide are present, and the amount of dibenzoyl peroxide and / or hydrogen peroxide ranges between 0.1 wt% and 15 wt%, preferably between 1-10 wt%, more preferably between 1-5wt% relative to the weight of the thermoplastic polymer solution. 5) The method according to any one of the preceding claims, wherein a salt is present and the salt is preferably selected from sodium chloride, potassium chloride, calcium chloride, copper sulfate, ferrous sulfate, lithium chloride, magnesium sulfate, potassium iodide, sodium acetate, calcium acetate or mixtures thereof. 6) The method according to any one of the preceding claims, wherein the salt is selected from lithium chloride, calcium chloride, ferrous sulfate, potassium iodide or mixtures thereof, and wherein the amount of salt ranges preferably between 0.1 wt% and 30 wt%, more preferably between 1-15 wt%, more preferably between 2-8 wt% relative to the weight of the thermoplastic polymer solution. 7) The method according to any one of the preceding claims, wherein an acid is present, and the acid is selected from acetic acid, hydrochloric acid, sulfuric acid, nitric acid, dichloroacetic acid, formic acid, hydrofluoric acid, phosphoric acid, citric acid, carbonic acid or mixtures thereof. RENOV24001NL / P0 -22- 8) The method according to any one of the preceding claims, wherein the thermoplastic polymer is selected from polystyrene, polyamide, acrylonitrile butadiene styrene, polyethylene terephthalate, polylactide and polyimide, preferably the thermoplastic polymer is a polyamide. 9) The method according to any one of the preceding claims, wherein the solvent is chosen from N-Methyl-2-pyrrolidone, xylenes, dimethyl sulfoxide, dimethyl formamide, dimethyl acetamide, diethyl ether, isopropyl alcohol, butyl alcohol, acetonitrile, ethylene dichloride, ethyl acetate, ethylene glycol, formic acid, tetrahydrofuran, esters, ethanol, acetone, dioxane, chloroform, phenol, toluene, nitrobenzene, dichloromethane, benzoyl chloride, benzene, pyridine, butyl acetate, nitrobenzene, hexane, acetonitrile, acetic acid, methanol, water or mixtures thereof. 10)The method according to anyone of the preceding claims wherein the thermoplastic polymer and solvents are chosen from the combinations: polyamide (PA) with the solvent formic acid, and a solution of CaCI2 or LiCl in ethanol or methanol; acrylonitrile butadiene styrene (ABS) with a solvent chosen from esters, ketones (such as acetone), chloroform, ethylene dichloride; polyethylene terephthalate (PET) with a solvent chosen from phenol, trifluoroacetic acid, o-chlorophenol, tetrachlorethane, nitrobenzene; polylactide (PLA) with a solvent chosen from dioxane, acetonitrile, chloroform, methylene chloride, 1,1,2- trichloroethane, dichloroacetic acid. 11)The method according to any one of the preceding claims, wherein the amount of aniline ranges between 0.5wt% and 50 wt% relative to the amount of thermoplastic polymer. 12)The method according to any one of the preceding claims, wherein polyaniline is preferably in the form of leucomeraldine, emeraldine or pernigraniline, more preferably in the form of protonated emeraldine. 13)The method according to any one of the preceding claims, wherein temperatures during polymerization of aniline is maintained lower than: (1) crystallization temperature of the thermoplastic polymer; (2) boiling temperature of the polymer solvent. 14)A masterbatch comprising a thermoplastic polymer and a polyaniline (PANI), wherein the PANI is present as a dispersed phase in a form of particles with the size range between 1 and 250 nm. 15)The masterbatch according to claim 11, wherein the thermoplastic polymer is a polyamide, acrylonitrile butadiene styrene, polyethylene terephthalate or polylactide, and wherein at least70% of particles of PANI have a size range between 3 nm and 150 nm. 16)The masterbatch according to claim 11 or 12, wherein the amount of PANI ranges between 1 and 25 wt%, preferably the amount of PANI ranges between 3 and 15 wt%, more preferably the amount of PANI ranges between 4 and 8 wt%, relative to the weight of the masterbatch. RENOV24001NL / P0 -23- 17)The masterbatch according to any one of claims 11-13, wherein the thermoplastic polymer is selected from polyamide 6, polyamide 6-6, polyamide 4-6, polyamide 6-10, alcohol-soluble polyamide resin, polyamide 11, polyamide 12, polyamide 6-12, polyamide 6-9, polyamide 6-10, polyamide 12-12, polyphthalamide. 18)A thermoplastic composite comprising a polymer selected from polyethylene terephthalate, thermoplastic polyurethane, polypropylene, polyethylene, polystyrene, acrylonitrile butadiene styrene, polyvinyl chloride, polylactide, polyphenylene sulfide, polyphthalamide, polybutylene terephthalate, polyimide, polyether ether ketone, polytetrafluoroethylene , polyetherimide, polyvinyl alcohol and polyamide and the masterbatch as obtained in any one of claims 1-10 or as defined in any one of claims 11 to 14. 19)The thermoplastic composite according to claim 15, wherein the concentration of PANI ranges between 0.0001 and 0.4 wt%, preferably the concentration of PANI ranges between 0.001 and 0.3 wt%, more preferably the concentration of PANI ranges between 0.01 and 0.15 wt%. 20)A method of preparing the thermoplastic composite according to any one of claims 15 or 16, by coextrusion of a polymer selected from polyethylene terephthalate, thermoplastic polyurethane, polypropylene, polyethylene, polystyrene, acrylonitrile butadiene styrene, polyvinyl chloride, polylactide, polyphenylene sulfide, polyphthalamide, polybutylene terephthalate, polyimide, polyether ether ketone, polytetrafluoroethylene , polyetherimide, polyvinyl alcohol and polyamide; with the masterbatch as obtained in any one of claims 1- 10 or as defined in any one of claims 11 to 14. RENOV24001NL / P0 -24-

Claims

1) A method for preparing a masterbatch consisting of a thermoplastic polymer and polyaniline, consisting of the following steps a) Dissolving a thermoplastic polymer in a suitable solvent to a to obtain thermoplastic polymer solution; b) Adding aniline to the thermoplastic polymer solution; c) Optionally, adding a salt, acid, oxidizing agent and water to the solution of step b), resulting in polymerization of aniline to polyaniline (PANI) induced to a dissolved mixture of thermoplastic polymer and PANI to acquire; d) Coagulate the dissolved mixture of thermoplastic polymer and PANI to a masterbatch of thermoplastic polymer with PANI is available. 2) The method according to claim 1 where the oxidizing agent is an oxidation salt and the oxidation salt is selected from sodium and potassium chlorate, potassium permanganate, potassium dichromate or ammonium persulfate. 3) The method according to one of the preceding claims, whereby the quantity Oxidizing salt lies between 0.1 wt% and 30 wt%, preferably between 1-15 wt%, more at preference between 2-8 wt% relative to the weight of the thermoplastic polymer solution. 4) The method according to one of the preceding claims, in which as oxidizing agents dibenzoyl peroxide and / or hydrogen peroxide are present, and the amount dibenzoyl peroxide and / or hydrogen peroxide is between 0.1 and 15 wt%, preferably between 1-10 wt%, more preferably between 1-5 wt% relative to the weight of the thermoplastic polymer solution. 5) The method according to one of the preceding claims, in which a salt is present and the salt is preferably chosen from sodium chloride, potassium chloride, calcium chloride, copper sulfate, iron sulfate, lithium chloride, magnesium sulfate, potassium iodide, sodium acetate, calcium acetate or mixtures thereof. 6) The method according to one of the preceding conclusions, in which the salt is selected of lithium chloride, calcium chloride, iron sulfate, potassium iodide or mixtures thereof, and in which the salt content lies between 0.1 and 30 wt%, preferably between 1-15 wt%, more, preferably between 2-8 wt% relative to the weight of the thermoplastic polymer solution. 7) The method according to one of the preceding claims, in which an acid is present, and the acid is chosen from acetic acid, hydrochloric acid, sulfuric acid, nitric acid, RENOV24001NL / P0 -25- dichloroacetic acid, formic acid, hydrofluoric acid, phosphoric acid, citric acid, carbonic acid or mixtures thereof. 8) The method according to one of the preceding claims, whereby the thermoplastic The polymer is selected from polystyrene, polyamide, or acrylonitrile butadiene styrene. polyethylene terephthalate, polylactide and polyimide, preferably the thermoplastic polymer a polyamide. 9) The method according to one of the preceding claims, in which the solvent is selected from N-methyl-2-pyrrolidone, xylenes, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, diethyl ether, isopropyl alcohol, butyl alcohol, acetonitrile, ethylene dichloride, ethyl acetate, ethylene glycol, formic acid, tetrahydrofuran, esters, ethanol, acetone, dioxane, chloroform, phenol, toluene, nitrobenzene, dichloromethane, benzoyl chloride, benzene, pyridine, butyl acetate, nitrobenzene, hexane, acetonitrile, acetic acid, methanol, water or mixtures thereof. 10) The method according to one of the preceding conclusions whereby the thermoplastic polymer and the solvents are selected from the combinations of polyamide (PA) with the solvent formic acid and a solution of CaCl2 or LiCl in ethanol or methanol; acrylonitrile butadiene styrene (ABS) with a solvent chosen from esters, ketones (such as acetone), chloroform, ethylene dichloride; polyethylene terephthalate (PET) with a solvent selected from phenol, trifluoroacetic acid, o-chlorophenol, tetrachloroethane, nitrobenzene; polylactide (PLA) with a solvent chosen from dioxane, acetonitrile, chloroform, methylene chloride, 1,1,2-trichloroethane, dichloroacetic acid. 11) The method according to one of the preceding claims, whereby the amount of aniline lies between 0.5 and 50 weight percent of the amount of thermoplastic polymer. 12) The method according to one of the preceding conclusions, whereby polyaniline at preferably in the form of leucomeraldine, emeraldine or pernigraniline, preferably in the form of protonated emeraldine. 13) The method according to one of the preceding conclusions, whereby the temperature during the polymerization of aniline is kept lower than: 1) the crystallization temperature of the thermoplastic polymer; 2) the boiling temperature of the polymer solvent. 14) A masterbatch consisting of a thermoplastic polymer and a polyaniline (PANI), in which the PANI is present as a dispersed phase in the form of particles with a size between 1 and 250 nm, as determined by TEM. 15) The masterbatch referred to in claim 11, in which the thermoplastic polymer a polyamide, acrylonitrile butadiene styrene, polyethylene terephthalate or polylactide is, and in which at least 70% of the PANI particles have a size range between 3 nm and 150 nm has. RENOV24001NL / P0 -26- 16) The masterbatch under claim 11 or 12, in which the quantity PANI varies between 1 and 25 wt%, preferably the amount of PANI varies between 3 and 15 wt%, more preferably the amount of PANI varies between 4 and 8 wt%, compared to the weight of the masterbatch. 17) The masterbatch according to one of claims 11-13, where the thermoplastic The polymer is selected from polyamide 6, polyamide 6-6, polyamide 4-6, and polyamide 6- 10, alcohol-soluble polyamide resin, polyamide 11, polyamide 12, polyamide 6-12, polyamide 6-9, polyamide 6-10, polyamide 12-12, polyphthalamide. 18) A thermoplastic composite consisting of a polymer selected from polyethylene terephthalate, thermoplastic polyurethane, polypropylene, polyethylene, polystyrene, acrylonitrile butadiene styrene, polyvinyl chloride, polylactide, polyphenylene sulfide, polyphthalamide, polybutylene terephthalate, polyimide, polyetheretherketone, polytetrafluoroethylene, polyetherimide, polyvinyl alcohol and polyamide and the masterbatch as obtained in any of claims 1 to 10 or as defined in one of Conclusions 11 to 14. 19) The thermoplastic composite according to claim 15, in which the PANI concentration lies between 0.0001 and 0.4 wt%, preferably the PANI concentration lies between 0.001 and 0.3 wt%, preferably the PANI concentration lies between 0.01 and 0.15 wt%. 20) A method for preparing the thermoplastic composite according to one of the claims 15 or 16, by coextrusion of a polymer from polyethylene terephthalate, thermoplastic polyurethane, polypropylene, polyethylene, polystyrene, acrylonitrile butadiene styrene, polyvinyl chloride, polylactide, polyphenylene sulfide, polyphthalamide, polybutylene terephthalate, polyimide, polyetheretherketone, polytetrafluoroethylene, polyetherimide, polyvinyl alcohol and polyamide; with the masterbatch as obtained in one of the claims 1-10 or as described in a of conclusions 11 to 14. RENOV24001NL / P0 1 / 5 Figure 1 Figure 2 RENOV24001NL / P0 2 / 5 Figure 3 Figure 4 RENOV24001NL / P0 3 / 5 Figure 5 RENOV24001NL / P0 4 / 5 Figure 6 Figure 7 RENOV24001NL / P0 5 / 5 Figure 8 Figure 9

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