Polymer composite, method for modulating the properties of a polymer matrix, use of the polymer composite and use of metal particles

Abstract

The present invention relates to the fields of chemistry, nanotechnology and materials engineering, and discloses a polymer composite comprising at least one polymer matrix and at least one filler consisting of metal particles. The invention also discloses a method for modulating the properties of a polymer matrix comprising incorporating a filler consisting of metal particles into the polymer matrix. One of the advantages offered by the invention is that of extending the service life of polymers or restoring the properties of a recycled polymer to a state comparable to that of virgin polymer; furthermore, it improves the material's efficiency and cost-effectiveness, resulting in gains in hydrophobicity, weather and UV resistance, and mechanical, thermal and physicochemical properties, thereby expanding its applicability and added value. The invention also describes use of the aforementioned polymer composite and the use of metal particles to restore the properties of a recycled polymer matrix to the virgin state thereof.

Description

Polymer composite, method for modulating the properties of a polymer matrix, use of polymer composite and use of metallic particles. Field of Invention

[0001] The present invention is situated in the fields of Chemistry, Nanotechnology and Materials Engineering, revealing a polymeric composite comprising at least one polymeric matrix and at least one filler of metallic particles. The invention also reveals a method for modulating the properties of a polymeric matrix comprising incorporating a filler of metallic particles into the polymeric matrix. One of the advantages provided by the invention is to extend the lifespan of polymers or restore the properties of a recycled polymer to levels comparable to the polymer in its virgin form. Furthermore, it offers improved efficiency and cost-effectiveness of the material, resulting in gains in hydrophobicity, weather and UV resistance, mechanical, thermal, and physicochemical properties; expanding applicability and added value.The invention also defines the use of said polymer composite and the use of metallic particles to restore the properties of a recycled polymer matrix to its virgin state. Background of the Invention

[0002] Nanoscience encompasses the study of materials at the nanoscale, while nanotechnology refers to the technological application of these materials, which can be done at the atomic or molecular level, to create large, highly organized structures, aiming to produce new materials and devices with unique properties (Netravali and Mittal, 2017).

[0003] Nanomaterial production can be carried out using either the "bottom-up" or "top-down" method. Techniques using the "bottom-up" method involve producing nanostructures built atom by atom, while Techniques that utilize a "top-down" approach aim to obtain nanomaterials from macroscopic scale materials, producing them from "macro to nano" (Netravali and Mittal, 2017).

[0004] Polymers are macromolecules formed by many repeating units chemically linked together by covalent bonds. Currently, there is a search for polymers combined with other types of materials, resulting in composite materials with improved properties for applications in engineering, medicine, food, and other fields. In the area of ​​materials applied to food, polymer nanocomposites can be used as barrier materials for food, helping to increase its shelf life and potentially making it safer. Polymer nanocomposites also show great potential in different biomedical applications; however, when applied to this area, the material must exhibit some specific properties, such as biodegradability and biocompatibility. Polymer nanocomposites can also be widely applied in electrochemical, optical, and electrical sensors and biosensors (Netravali and Mittal, 2017).

[0005] The search for materials with optimized properties for applications in diverse areas has led to the widespread use of composite materials. These are produced by combining two or more materials with distinct physical and / or chemical properties, resulting in a multiphase material with characteristics distinct from the constituent phases and superior final performance due to the optimized combination of properties. Composite materials can be based on polymeric matrices, ceramic matrices, or even metallic matrices.

[0006] Composite materials combine properties of the continuous phase (matrix) and the dispersed phase (filler), providing significant improvements; the transition to nanoparticles impacts the properties of the materials, resulting in nanocomposites with improvements in thermal, chemical, mechanical, and physical properties when compared to composites. conventional methods. These improvements are achieved by the appropriate incorporation of nanoparticles into the polymer system, according to the ideal content of each type of nanoparticle (GODARA et al., 2021; GDOUTS, 2020; SEYYED et al., 2020).

[0007] In the search for the state of the art in scientific and patent literature, the following documents were found that address the topic:

[0008] The Netravali and Mittal document from 2017 reveals the definitions and historical context of the techniques used. However, that document does not describe a nanostructured polymer composite as described in the present patent application.

[0009] The Dong and Gauvin document from 1993 discloses the preparation of polypropylene fibers modified with mercaptan groups and their use in composites with epoxy resin. However, that document does not disclose a nanostructured polymer composite like the one in the present patent application.

[0010] The invention solves the problem of efficiency and cost-effectiveness by modulating the properties of polymeric matrices, resulting in gains in hydrophobicity, weather and UV resistance, mechanical properties, among other properties.

[0011] Additionally, the invention solves the problem of loss of properties in recycled thermoplastic polymers, which lose significant physical, chemical, and mechanical properties after at least one processing or use cycle. It also addresses the problem of restoring the lost properties of recycled polymers when compared to polymers in their virgin state.

[0012] Based on the literature reviewed, no documents were found that anticipated or suggested the teachings of the present invention, so the solution proposed here is, in the eyes of the inventors, novel and inventive compared to the state of the art. Summary of the Invention

[0013] The inventors developed a polymer composite with optimized properties, high efficiency, and improved cost-effectiveness, using... A metallic particle load and a polymeric matrix, incorporating the metallic particle load into the polymeric matrix. The advantage provided also lies in gains in hydrophobicity, weather and UV resistance, mechanical, thermal, and physicochemical properties; expanding applicability and added value. Furthermore, another advantage of the present invention is the ability to extend the service life of polymers and / or return the properties of a recycled polymeric matrix to its virgin state.

[0014] In a first aspect, the present invention discloses a polymeric composite comprising: at least one polymeric matrix; and at least one filler of metallic particles, wherein said polymeric matrix comprises thermoplastic elastomer, thermoplastic polymer or combinations thereof, and wherein said metallic species comprises niobium, tantalum, titanium, hafnium, zirconium, cerium or combinations thereof.

[0015] In a second aspect, the present invention provides a method for modulating the properties of a polymeric matrix comprising at least one step of incorporating metallic particle filler into a polymeric matrix, wherein said polymeric matrix comprises thermoplastic elastomer, thermoplastic polymer or combinations thereof, and wherein said metallic species comprises niobium species, tantalum species, titanium species, hafnium species, zirconium species, cerium species or combinations thereof.

[0016] In a third aspect, the present invention presents a use of the polymer composite as a structural, functional or finishing component.

[0017] In a fourth aspect, the present invention provides for the use of metallic particles to restore the properties of a recycled polymer matrix to its virgin state, comprising at least one step of incorporating metallic particles into a recycled polymer matrix, wherein said polymer matrix comprises thermoplastic elastomer, thermoplastic polymer or combinations thereof, wherein the said metallic species comprises a species of Niobium, a species of Tantalum, a species of Titanium, a species of Hafnium, a species of Zirconium, a species of Cerium or combinations thereof.

[0018] These and other objects of the invention will be immediately appreciated by those skilled in the art and will be described in detail below. Brief Description of the Figures

[0019] The following figures are presented:

[0020] Figure 1 shows the results of the storage module (E') DMA analysis for sample R86 of PU resin with niobium pentoxide nanoparticles at a concentration of 50 ppm, comparing standard resin, resin with nanoparticles, and resin with nanoparticles and AMP-95.

[0021] Figure 2 shows the results of the storage module (E') of DMA analysis for sample R86 of PU resin with niobium pentoxide nanoparticles at a concentration of 100 ppm, comparing standard resin, resin with nanoparticles, and resin with nanoparticles and AMP-95.

[0022] Figure 3 shows the results of the storage module (E') of DMA analysis for sample R86 of PU resin with niobium pentoxide nanoparticles at a concentration of 200 ppm, comparing standard resin, resin with nanoparticles, and resin with nanoparticles and AMP-95.

[0023] Figure 4 shows the results of the loss modulus (E”) of DMA analysis for sample R86 of PU resin with niobium pentoxide nanoparticles at a concentration of 50 ppm, comparing standard resin, resin with nanoparticles, and resin with nanoparticles and AMP-95.

[0024] Figure 5 shows the results of the loss modulus (E”) of DMA analysis for sample R86 of PU resin with niobium pentoxide nanoparticles at a concentration of 100 ppm, comparing standard resin, resin with nanoparticles, and resin with nanoparticles and AMP-95.

[0025] Figure 6 shows the results of the loss module (E”) of the DMA analysis. For sample R86 of PU resin with niobium pentoxide nanoparticles at a concentration of 200 ppm, comparing standard resin, resin with nanoparticles, and resin with nanoparticles and AMP-95.

[0026] Figure 7 shows the results of the damping factor (Tan õ) from DMA analysis for sample R86 of PU resin with niobium pentoxide nanoparticles at a concentration of 50 ppm, comparing standard resin, resin with nanoparticles, and resin with nanoparticles and AMP-95.

[0027] Figure 8 shows the results of the damping factor (Tan õ) from DMA analysis for sample R86 of PU resin with niobium pentoxide nanoparticles at a concentration of 100 ppm, comparing standard resin, resin with nanoparticles, and resin with nanoparticles and AMP-95.

[0028] Figure 9 shows the results of the damping factor (Tan õ) from DMA analysis for sample R86 of PU resin with niobium pentoxide nanoparticles at a concentration of 200 ppm, comparing standard resin, resin with nanoparticles, and resin with nanoparticles and AMP-95.

[0029] Figure 10 shows the results of the storage module (E') of DMA analysis for R92 samples of PU resin with niobium pentoxide nanoparticles at concentrations of 50 ppm, 100 ppm and 200 ppm compared with the standard resin, wherein the nanoparticles were functionalized with AMP-95.

[0030] Figure 11 shows the results of the loss modulus (E”) of DMA analysis for R92 samples of PU resin with niobium pentoxide nanoparticles at concentrations of 50 ppm, 100 ppm and 200 ppm compared with the standard resin, where the nanoparticles were functionalized with AMP-95.

[0031] Figure 12 shows the results of the damping factor (Tan õ) from DMA analysis for R92 samples of PU resin with niobium pentoxide nanoparticles at concentrations of 50 ppm, 100 ppm and 200 ppm compared to the standard resin, where the nanoparticles were functionalized with AMP-95.

[0032] Figure 13 shows a summarized flowchart of the process for obtaining of nanoparticles functionalized with APTES.

[0033] Figure 14 shows a summary flowchart of the process for obtaining nanoparticles functionalized with Glycidyl-POSS.

[0034] Figure 15 shows the results of the storage module in DMA analysis for TPU + nanoparticle samples compared to virgin TPU (obtained at 1 Hz).

[0035] Figure 16 shows the loss modulus results in DMA analysis for TPU + nanoparticle samples compared to virgin TPU (obtained at 1 Hz).

[0036] Figure 17 shows the damping factor results in DMA analysis for TPU + nanoparticle samples compared to virgin TPU (obtained at 1 Hz).

[0037] Figure 18 shows the results of the storage module in DMA analysis for TPU samples + APTES-functionalized nanoparticles compared to virgin TPU (obtained at 1 Hz).

[0038] Figure 19 shows the loss modulus results in DMA analysis for TPU samples + APTES-functionalized nanoparticles compared to virgin TPU (obtained at 1 Hz).

[0039] Figure 20 shows the damping factor results in DMA analysis for TPU samples + APTES-functionalized nanoparticles compared to virgin TPU (obtained at 1 Hz).

[0040] Figure 21 shows the results of the storage module in DMA analysis for TPU samples + nanoparticles functionalized with Glycidyl-POSS compared to virgin TPU (obtained at 1 Hz).

[0041] Figure 22 shows the loss modulus results in DMA analysis for TPU samples + Glycidyl-POSS functionalized nanoparticles compared to virgin TPU (obtained at 1 Hz).

[0042] Figure 23 shows the damping factor results in DMA analysis for TPU samples + nanoparticles functionalized with Glycidyl-POSS compared to virgin TPU (obtained at 1 Hz).

[0043] Figure 24 shows the Heat Flow (ua) vs. Temperature (°C) graph characterizing the extrusion of the control samples and samples with non-functionalized Nb nanoparticles after the 1st step. o and the 2 o heating.

[0044] Figure 25 shows the Heat Flow (ua) versus Temperature (°C) graph characterizing the extrusion of the control samples and samples with APTES-functionalized Nb nanoparticles after the 1st o and the 2 o heating.

[0045] Figure 26 shows the Heat Flow (ua) versus Temperature (°C) graph characterizing the extrusion of the control samples and samples with Nb nanoparticles functionalized with POSS after the 1st o and the 2 o heating.

[0046] Figure 27 shows the Heat Flow (ua) versus Temperature (°C) graph characterizing the injection of control samples and samples with non-functionalized Nb nanoparticles after the 1st o and the 2 o heating.

[0047] Figure 28 shows the Heat Flow (ua) versus Temperature (°C) graph characterizing the injection of control samples and samples with APTES-functionalized Nb nanoparticles after the 1st o and the 2 o heating.

[0048] Figure 29 shows the Heat Flow (ua) versus Temperature (°C) graph characterizing the injection of control samples and samples with Nb nanoparticles functionalized with POSS after the 1st o and the 2 o heating.

[0049] Figure 30 shows the graph of the T values. g of the control samples and those with non-functionalized Nb, after extrusion and injection.

[0050] Figure 31 shows the graph of the T values. g of the control samples and those with Nb functionalized with APTES, after extrusion and injection.

[0051] Figure 32 shows the graph of the T values. g of the control samples and with Nb functionalized with POSS, after extrusion and injection.

[0052] Fig. 33 shows the graph with the values ​​of the modulus of elasticity (MPa) of virgin TPU samples and with non-functionalized Nb nanoparticles and functionalized with APTES and POSS.

[0053] Fig. 34 shows the graph with the values ​​of stress and elongation at break of virgin TPU samples and with non-functionalized Nb nanoparticles and functionalized with APTES and POSS.

[0054] Fig. 35 shows the mass percentage vs. temperature (°C) graph characterizing the extrusion of TPU samples and TPU with 50, 200, and 800 ppm of Nb nanoparticles.

[0055] Fig. 36 shows the DTG (% / °C) vs. temperature (°C) graph characterizing the extrusion of TPU samples and TPU with 50, 200, and 800 ppm of Nb nanoparticles.

[0056] Fig. 37 shows the mass percentage vs. temperature (°C) graph characterizing the extrusion of TPU samples and TPU with 50, 200, and 800 ppm of Nb nanoparticles functionalized with APTES.

[0057] Fig. 38 shows the DTG (% / °C) vs. temperature (°C) graph characterizing the extrusion of TPU samples and TPU with 50, 200, and 800 ppm of Nb nanoparticles functionalized with APTES.

[0058] Fig. 39 shows the mass percentage vs. temperature (°C) graph characterizing the extrusion of TPU samples and TPU with 50, 200, and 800 ppm of Nb nanoparticles functionalized with POSS.

[0059] Fig. 40 shows the DTG (% / °C) vs. temperature (°C) graph characterizing the extrusion of TPU samples and TPU with 50, 200, and 800 ppm of Nb nanoparticles functionalized with POSS.

[0060] Fig. 41 shows the mass percentage vs. temperature (°C) graph characterizing the injection of TPU samples and TPU with 50, 200, and 800 ppm of Nb nanoparticles.

[0061] Fig. 42 shows the DTG (% / °C) vs. temperature (°C) graph characterizing the injection of TPU samples and TPU with 50, 200, and 800 ppm of Nb nanoparticles.

[0062] Fig. 43 shows the mass percentage vs. temperature (°C) graph characterizing the injection of TPU samples and TPU with 50, 200, and 800 ppm of Nb nanoparticles functionalized with APTES.

[0063] Fig. 44 shows the DTG (% / °C) vs. temperature (°C) graph characterizing the injection of TPU samples and TPU with 50, 200, and 800 ppm of Nb nanoparticles functionalized with APTES.

[0064] Fig. 45 shows the mass percentage vs. temperature (°C) graph characterizing the injection of TPU samples and TPU with 50, 200, and 800 ppm of Nb nanoparticles functionalized with POSS.

[0065] Fig. 46 shows the DTG (% / °C) vs. temperature (°C) graph characterizing the injection of TPU samples and TPU with 50, 200, and 800 ppm of Nb nanoparticles functionalized with POSS.

[0066] Fig. 47 shows the hardness graph (Shore A) of TPU samples and TPU with 50, 200 and 800 ppm of non-functionalized and APTES- and POSS-functionalized Nb nanoparticles.

[0067] Fig. 48 shows the tear strength graph (kN / m) of TPU samples and TPU with 50, 200 and 800 ppm of non-functionalized and APTES- and POSS-functionalized Nb nanoparticles.

[0068] Figure 49 shows the graph Log cp x 1 / T (K -1 ), of the TPU samples without Nb nanoparticles.

[0069] Fig. 50 shows the temperature-to-water conversion graph (°C) for TPU samples without Nb nanoparticles.

[0070] Figure 51 shows the graph Log cp x 1 / T (K -1 ), of the TPU samples with non-functionalized Nb nanoparticles.

[0071] Fig. 52 shows the temperature-to-energy conversion graph (°C) of TPU samples with non-functionalized Nb nanoparticles.

[0072] Fig. 53 shows the activation energy graph of TPU samples without nanoparticles and with non-functionalized and functionalized Nb nanoparticles with POSS and APTES.

[0073] Fig. 54 shows the stress (MPa) vs. time (h) graph of TPU samples without nanoparticles and with non-functionalized and functionalized Nb nanoparticles with POSS and APTES.

[0074] Fig. 55 shows the percentage deformation vs. time (h) graph of TPU samples without nanoparticles and with non-functionalized and functionalized Nb nanoparticles with POSS and APTES.

[0075] Figure 56 shows the graphs of E' (MPa) vs. temperature (°C) for the samples. Repurposed TPU without nanoparticles and with non-functionalized and functionalized Nb nanoparticles with POSS and APTES, in different temperature ranges.

[0076] Fig. 57 shows the graphs of E” (MPa) x temperature (°C) of the recycled TPU samples without nanoparticles and with non-functionalized and functionalized Nb nanoparticles with POSS and APTES, in different temperature ranges.

[0077] Fig. 58 shows the Tan õ x temperature (°C) graphs of the recycled TPU samples without nanoparticles and with non-functionalized and functionalized Nb nanoparticles with POSS and APTES, in different temperature ranges.

[0078] Figure 59 shows the E' graph at 23°C (MPa) of the recycled TPU and reference TPU samples, with and without non-functionalized and functionalized Nb nanoparticles. The arrows indicate the axis corresponding to each curve.

[0079] Fig. 60 shows the AVrel abrasion graph (mm 3 ) of reprocessed and reference TPU samples with and without functionalized and non-functionalized Nb nanoparticles.

[0080] Fig. 61 shows the hardness graph (Shore A) of the reprocessed and reference TPU samples with and without functionalized and non-functionalized Nb nanoparticles.

[0081] Fig. 62 shows the stress (MPa) vs. strain (%) graph of reprocessed and reference TPU samples with and without functionalized and non-functionalized Nb nanoparticles.

[0082] Fig. 63 shows the modulus of elasticity graph, E (MPa) 50%, 100%, 200% and 300% of TPU samples with and without functionalized and non-functionalized nanoparticles.

[0083] Fig. 64 shows the stress-at-break (MPa) graph of the reference and reprocessed TPU samples, with and without functionalized and non-functionalized Nb nanoparticles.

[0084] Fig. 65 shows the elongation at break (%) graph of the reference and reprocessed TPU samples, with and without functionalized and non-functionalized Nb nanoparticles.

[0085] Fig. 66 shows the tear strength graph (kN / m) of the reference and reprocessed TPU samples, with and without functionalized and non-functionalized Nb nanoparticles.

[0086] Fig. 67 shows the graph of length variation (%) of the reference and reprocessed TPU samples, with and without functionalized and non-functionalized Nb nanoparticles.

[0087] Fig. 68 shows the graph of variation in width (%) of the reference and reprocessed TPU samples, with and without functionalized and non-functionalized Nb nanoparticles.

[0088] Fig. 69 shows the colorimetry graph of the non-aged reference and reprocessed TPU samples, with and without functionalized and non-functionalized Nb nanoparticles.

[0089] Fig. 70 shows the colorimetry graph of samples aged for 500h of reference TPU and reprocessed TPU, with and without functionalized and non-functionalized Nb nanoparticles.

[0090] Fig. 71 shows the FTIR spectrum of TPU pellets after 1 processing and after 3 processing.

[0091] Fig. 72 shows the FTIR spectrum of TPU pellets with Nb nanoparticles after 1 processing and after 3 processing.

[0092] Fig. 73 shows the FTIR spectrum of TPU pellets with APTES-functionalized Nb nanoparticles after 1 processing and after 3 processing cycles.

[0093] Fig. 74 shows the FTIR spectrum of TPU pellets with POSS-functionalized Nb nanoparticles after 1 processing and after 3 processing cycles.

[0094] Figure 75 shows the TGA analysis graphs of the TPU samples without nanoparticles after 1 processing and after 3 processing cycles. The graph TPU 3P shows the deconvolution of the 3P curves, to confirm the TPU degradation peaks.

[0095] Figure 76 shows the TGA analysis graphs of TPU samples with Nb nanoparticles after 1 processing and after 3 processing cycles. The TPU 3P graph shows the deconvolution of the 3P curves, confirming the TPU degradation peaks, which did not show significant changes.

[0096] Figure 77 shows the TGA analysis graphs of TPU samples with APTES-functionalized Nb nanoparticles after 1 processing and after 3 processing cycles. The TPU 3P graph shows the deconvolution of the 3P curves, confirming the TPU degradation peaks.

[0097] Figure 78 shows the TGA analysis graphs of TPU samples with POSS-functionalized Nb nanoparticles after 1 processing and after 3 processing cycles. The TPU 3P graph shows the deconvolution of the 3P curves, confirming the TPU degradation peaks.

[0098] Fig. 79 shows the heat flow (ua) vs. temperature (°C) graphs of the 1 o and 2o Heating of TPU samples without nanoparticles after 1 and after 3 processing cycles.

[0099] Fig. 80 shows the heat flow (ua) vs. temperature (°C) graphs of the 1 o and 2 o Heating of TPU samples with Nb nanoparticles after 1 and after 3 processing cycles.

[0100] Fig. 81 shows the heat flow (ua) vs. temperature (°C) graphs of the 1 o and 2 o Heating of TPU samples with APTES-functionalized Nb nanoparticles after 1 and after 3 processing cycles.

[0101] Fig. 82 shows the heat flow (ua) vs. temperature (°C) graphs of the 1 o and 2 o Heating of TPU samples with POSS-functionalized Nb nanoparticles after 1 and after 3 processing cycles.

[0102] Fig. 83 shows the FTIR spectra of TPU and reprocessed TPU, before and after 500h of aging with xenon.

[0103] Fig. 84 shows the FTIR spectra of TPU and reprocessed TPU, with Nb nanoparticles, before and after 500h of aging with xenon.

[0104] Fig. 85 shows the FTIR spectra of TPU and reprocessed TPU, with Nb nanoparticles functionalized with APTES, before and after 500h of aging with xenon.

[0105] Fig. 86 shows the FTIR spectra of TPU and reprocessed TPU, with Nb nanoparticles functionalized with POSS, before and after 500h of aging with xenon.

[0106] Fig. 87 shows the graph of Ea (kJ / mol) x conversion (a) of aged TPU samples and TPU with non-functionalized and functionalized Nb nanoparticles with POSS and APTES.

[0107] Fig. 88 shows the graphs of E' at 23°C (MPa) and Tg (°C) of TPU samples with and without non-functionalized and functionalized Nb nanoparticles, before aging and after 500h of xenon aging.

[0108] Fig. 89 shows the mass percentage vs. temperature (°C) graphs of TPU and recycled TPU samples before aging and after 500h of xenon aging in the temperature range of 0 to approximately 650°C.

[0109] Fig. 90 shows the mass percentage vs. temperature (°C) graphs of TPU and recycled TPU samples before aging and after 500h of xenon aging in the temperature range of 0 to approximately 800°C.

[0110] Fig. 91 shows the mass percentage vs. temperature (°C) graphs of TPU samples with Nb nanoparticles and recycled TPU with Nb nanoparticles before aging and after 500h of xenon aging in the temperature range of 0 to approximately 650°C.

[0111] Fig. 92 shows the mass percentage vs. temperature (°C) graphs of TPU samples with Nb nanoparticles and recycled TPU with Nb nanoparticles before aging and after 500h of xenon aging in the temperature range of 0 to approximately 800°C.

[0112] Figure 93 shows the graphs of mass percentage versus temperature. (°C) of TPU samples with APTES-functionalized Nb nanoparticles and TPU with APTES-functionalized Nb nanoparticles repurposed before aging and after 500h of xenon aging in the temperature range of 0 to approximately 650°C.

[0113] Fig. 94 shows the mass percentage vs. temperature (°C) graphs of TPU samples with APTES-functionalized Nb nanoparticles and repurposed TPU with APTES-functionalized Nb nanoparticles before aging and after 500h of xenon aging in the temperature range of 0 to approximately 800°C.

[0114] Fig. 95 shows the mass percentage vs. temperature (°C) graphs of TPU samples with POSS-functionalized Nb nanoparticles and repurposed TPU with POSS-functionalized Nb nanoparticles before aging and after 500h of xenon aging in the temperature range of 0 to approximately 650°C.

[0115] Fig. 96 shows the mass percentage vs. temperature (°C) graphs of TPU samples with POSS-functionalized Nb nanoparticles and repurposed TPU with POSS-functionalized Nb nanoparticles before aging and after 500h of xenon aging in the temperature range of 0 to approximately 800°C.

[0116] Fig. 97 shows the heat flux (ua) vs. temperature (°C) graphs for TPU and reprocessed TPU samples before and after 500h of xenon aging.

[0117] Fig. 98 shows the heat flow (ua) vs. temperature (°C) graph of TPU and reprocessed TPU samples before and after 500h of xenon aging.

[0118] Fig. 99 shows the heat flux (ua) vs. temperature (°C) graph of TPU samples with Nb nanoparticles and TPU with Nb nanoparticles reprocessed before and after 500h of xenon aging.

[0119] Figure 100 shows the heat flow (ua) vs. temperature (°C) graph for TPU samples with Nb nanoparticles and TPU with Nb nanoparticles. reprocessed before and after 500 hours of xenon aging.

[0120] Fig. 101 shows the heat flux (ua) vs. temperature (°C) graph of TPU samples with APTES-functionalized Nb nanoparticles and TPU with APTES-functionalized Nb nanoparticles reprocessed before and after 500h of xenon aging.

[0121] Fig. 102 shows the heat flux (ua) vs. temperature (°C) graph of TPU samples with APTES-functionalized Nb nanoparticles and TPU with APTES-functionalized Nb nanoparticles reprocessed before and after 500h of xenon aging.

[0122] Fig. 103 shows the heat flux (ua) vs. temperature (°C) graph of TPU samples with POSS-functionalized Nb nanoparticles and TPU with POSS-functionalized Nb nanoparticles reprocessed before and after 500h of xenon aging.

[0123] Fig. 104 shows the heat flux (ua) vs. temperature (°C) graph of TPU samples with APTES-functionalized Nb nanoparticles and TPU with APTES-functionalized Nb nanoparticles reprocessed before and after 500h of xenon aging.

[0124] Fig. 105 shows the hardness graph (Shore A) of TPU samples and TPU with non-functionalized Nb nanoparticles and functionalized with APTES and POSS, before aging and after 1000h of xenon aging.

[0125] Fig. 106 shows the hardness graph (Shore A) of reprocessed TPU samples and TPU with non-functionalized Nb nanoparticles and functionalized with APTES and POSS before aging and after 1000h of xenon aging.

[0126] Fig. 107 shows the stress (MPa) vs. strain (%) graph of TPU samples and TPU with non-functionalized and APTES- and POSS-functionalized Nb nanoparticles before aging and after 1000h of xenon aging.

[0127] Figure 108 shows the stress (MPa) vs. strain (%) graph of reprocessed TPU and TPU samples with non-Nb nanoparticles. Functionalized and functionalized with APTES and POSS before aging and after 1000h of xenon aging.

[0128] Fig. 109 shows the E (MPa) graph of TPU samples, with and without non-functionalized and functionalized Nb nanoparticles, after 1000h of xenon aging.

[0129] Fig. 110 shows the E (MPa) graph of reprocessed TPU samples, with and without non-functionalized and functionalized Nb nanoparticles, after 1000h of xenon aging.

[0130] Fig. 111 shows the graph with the tensile strength (MPa) values ​​of the TPU samples and TPU with non-functionalized and APTES- and POSS-functionalized Nb nanoparticles, after 1000h of xenon aging.

[0131] Fig. 112 shows the graph with the tensile strength (MPa) values ​​of reprocessed TPU samples and TPU with non-functionalized Nb nanoparticles and functionalized with APTES and POSS, after 1000h of xenon aging.

[0132] Fig. 113 shows the graph with the elongation at break values ​​(%) of the TPU samples and TPU with non-functionalized and functionalized Nb nanoparticles with APTES and POSS, after 1000h of xenon aging.

[0133] Fig. 114 shows the graph with the elongation at break (%) values ​​of reprocessed TPU samples and TPU with non-functionalized and APTES- and POSS-functionalized Nb nanoparticles, after 1000h of xenon aging.

[0134] Fig. 115 shows the graph with the tear resistance values ​​(N / mm) of the TPU samples and TPU with non-functionalized and functionalized Nb nanoparticles with APTES and POSS, after 1000h of aging by xenon.

[0135] Figure 116 shows the graph with the tear resistance values ​​(N / mm) of the reprocessed TPU and TPU samples with Nb nanoparticles. Non-functionalized and functionalized with APTES and POSS, after 1000h of xenon aging.

[0136] Figure 117 shows the graph with the AVrel values ​​(mm 3 ) of TPU samples and TPU with non-functionalized and APTES- and POSS-functionalized Nb nanoparticles, after 1000h of xenon aging.

[0137] Figure 118 shows the graph with the AVrel values ​​(mm 3) of reprocessed TPU samples and TPU with non-functionalized and APTES- and POSS-functionalized Nb nanoparticles, after 1000h of xenon aging.

[0138] Fig. 119 shows the FTIR spectrum of TPU and reprocessed TPU samples, before and after 500h and 1000h of xenon aging.

[0139] Fig. 120 shows the FTIR spectrum of TPU samples with Nb nanoparticles and of TPU with reprocessed Nb nanoparticles, before and after 500h and 1000h of xenon aging.

[0140] Fig. 121 shows the FTIR spectrum of TPU samples with APTES-functionalized Nb nanoparticles and of TPU with APTES-functionalized Nb nanoparticles reprocessed, before and after 500h and 1000h of xenon aging.

[0141] Fig. 122 shows the FTIR spectrum of TPU samples with POSS-functionalized Nb nanoparticles and of TPU with reprocessed POSS-functionalized Nb nanoparticles, before and after 500h and 1000h of xenon aging.

[0142] Fig. 123 shows the heat flow (ua) vs. temperature (°C) graph of TPU and reprocessed TPU samples, before and after 500h and 1000h of xenon aging.

[0143] Fig. 124 shows the heat flow (ua) vs. temperature (°C) graph of TPU and reprocessed TPU samples, before and after 500h and 1000h of xenon aging.

[0144] Figure 125 shows the heat flux (ua) vs. temperature (°C) graph of TPU samples with Nb nanoparticles and TPU with Nb nanoparticles. reprocessed, before and after 500h and 1000h of xenon aging.

[0145] Fig. 126 shows the heat flow (ua) vs. temperature (°C) graph of TPU samples with Nb nanoparticles and reprocessed TPU with Nb nanoparticles, before and after 500h and 1000h of xenon aging.

[0146] Fig. 127 shows the heat flow (ua) vs. temperature (°C) graph of TPU samples with APTES-functionalized Nb nanoparticles and reprocessed TPU with APTES-functionalized Nb nanoparticles, before and after 500h and 1000h of xenon aging.

[0147] Fig. 128 shows the heat flow (ua) vs. temperature (°C) graph of TPU samples with APTES-functionalized Nb nanoparticles and reprocessed TPU with APTES-functionalized Nb nanoparticles, before and after 500h and 1000h of xenon aging.

[0148] Fig. 129 shows the heat flux (ua) vs. temperature (°C) graph of TPU samples with POSS-functionalized Nb nanoparticles and reprocessed TPU with POSS-functionalized Nb nanoparticles, before and after 500h and 1000h of xenon aging.

[0149] Fig. 130 shows the heat flow (ua) vs. temperature (°C) graph of TPU samples with POSS-functionalized Nb nanoparticles and reprocessed TPU with POSS-functionalized Nb nanoparticles, before and after 500h and 1000h of xenon aging.

[0150] Fig. 131 shows the E' graphs at 23°C (MPa) of the TPU and TPU samples with Nb nanoparticles without functionalization and functionalized with APTES and POSS, unprocessed and reprocessed, before and after 500h and 1000h of xenon aging.

[0151] Fig. 132 shows the E' (MPa) graph at different temperatures of TPU samples and TPU with Nb nanoparticles without functionalization and functionalized with APTES and POSS, not reprocessed, before and after 1000h of xenon aging.

[0152] Figure 133 shows a more detailed graph of E' (MPa) at -40°C for TPU samples and TPU with Nb nanoparticles without Functionalized and functionalized with APTES and POSS, not reprocessed, before and after 1000h of xenon aging.

[0153] Fig. 134 shows the Tg (°C) graphs of TPU samples and TPU with non-functionalized and APTES- and POSS-functionalized nanoparticles, both unreprocessed and reprocessed, before and after 500h and 1000h of xenon aging.

[0154] Fig. 135 shows the graph of variation in width and length (%) of TPU samples and TPU with non-functionalized Nb nanoparticles and functionalized with APTES and POSS, not reprocessed, after 1000h of xenon aging.

[0155] Fig. 136 shows the graph of variation in width and length (%) of TPU samples and TPU with non-functionalized and APTES- and POSS-functionalized Nb nanoparticles, reprocessed, after 1000h of xenon aging.

[0156] Fig. 137 shows the FTIR spectrum of TPU samples before and after 500h of UV aging and after 500h and 1000h of xenon aging.

[0157] Fig. 138 shows the FTIR spectrum of the reprocessed TPU samples before and after 500h of UV aging and after 500h and 1000h of xenon aging.

[0158] Fig. 139 shows the FTIR spectrum of TPU samples with Nb nanoparticles before and after 500h of UV aging and after 500h and 1000h of xenon aging.

[0159] Fig. 140 shows the FTIR spectrum of TPU samples with Nb nanoparticles, reprocessed, before and after 500h of UV aging and after 500h and 1000h of xenon aging.

[0160] Fig. 141 shows the FTIR spectrum of TPU samples with APTES-functionalized Nb nanoparticles, before and after 500h of UV aging and after 500h and 1000h of xenon aging.

[0161] Figure 142 shows the FTIR spectrum of the TPU samples with APTES-functionalized Nb nanoparticles, reprocessed, before and after 500h of UV aging and after 500h and 1000h of xenon aging.

[0162] Fig. 143 shows the FTIR spectrum of TPU samples with Nb nanoparticles functionalized with POSS, before and after 500h of UV aging and after 500h and 1000h of xenon aging.

[0163] Fig. 144 shows the FTIR spectrum of TPU samples with POSS-functionalized Nb nanoparticles, reprocessed, before and after 500h of UV aging and after 500h and 1000h of xenon aging.

[0164] Figure 145 shows the mass percentage vs. temperature (°C) graphs of unreprocessed and reprocessed TPU samples before and after 500h of UV aging and after 500h and 1000h of xenon aging.

[0165] Figure 146 shows the mass percentage vs. temperature (°C) graphs of unreprocessed and reprocessed TPU samples before and after 500h of UV aging and after 500h and 1000h of xenon aging.

[0166] Fig. 147 shows the mass percentage vs. temperature (°C) graphs of TPU samples with unreprocessed and reprocessed Nb nanoparticles before and after 500h of UV aging and after 500h and 1000h of xenon aging.

[0167] Fig. 148 shows the mass percentage vs. temperature (°C) graphs of the TPU samples with unreprocessed and reprocessed Nb nanoparticles before and after 500h of UV aging and after 500h and 1000h of xenon aging.

[0168] Fig. 149 shows the mass percentage vs. temperature (°C) graphs of TPU samples with APTES-functionalized Nb nanoparticles, both unreprocessed and reprocessed, before and after 500h of UV aging and after 500h and 1000h of xenon aging.

[0169] Figure 150 shows the mass percentage vs. temperature (°C) graphs of TPU samples with Nb nanoparticles functionalized with APTES, unprocessed and reprocessed, before and after 500h of UV aging and after 500h and 1000h of xenon aging.

[0170] Fig. 151 shows the mass percentage vs. temperature (°C) graphs of TPU samples with POSS-functionalized Nb nanoparticles, unprocessed and reprocessed, before and after 500h of UV aging and after 500h and 1000h of xenon aging.

[0171] Fig. 152 shows the mass percentage vs. temperature (°C) graphs of TPU samples with POSS-functionalized Nb nanoparticles, unprocessed and reprocessed, before and after 500h of UV aging and after 500h and 1000h of xenon aging.

[0172] Fig. 153 shows the heat flow (ua) vs. temperature (°C) graphs for the TPU samples, both unreprocessed and reprocessed, before and after 500h of UV aging and after 500h and 1000h of xenon aging.

[0173] Fig. 154 shows the heat flow (ua) vs. temperature (°C) graphs for the TPU samples, both unreprocessed and reprocessed, before and after 500h of UV aging and after 500h and 1000h of xenon aging.

[0174] Fig. 155 shows the heat flux (ua) vs. temperature (°C) graphs of TPU samples with Nb nanoparticles, unprocessed and reprocessed, before and after 500h of UV aging and after 500h and 1000h of xenon aging.

[0175] Fig. 156 shows the heat flow (ua) vs. temperature (°C) graphs of TPU samples with Nb nanoparticles, unprocessed and reprocessed, before and after 500h of UV aging and after 500h and 1000h of xenon aging.

[0176] Fig. 157 shows the heat flux (ua) vs. temperature (°C) graphs of the TPU samples with APTES-functionalized Nb nanoparticles, both unreprocessed and reprocessed, before and after 500h of UV aging and after 500h and 1000h of xenon aging.

[0177] Figure 158 shows the heat flow (ua) vs. temperature (°C) graphs of TPU samples with Nb nanoparticles functionalized with APTES. unprocessed and reprocessed, before and after 500h of UV aging and after 500h and 1000h of xenon aging.

[0178] Fig. 159 shows the heat flux (ua) vs. temperature (°C) graphs of TPU samples with POSS-functionalized Nb nanoparticles, unprocessed and reprocessed, before and after 500h of UV aging and after 500h and 1000h of xenon aging.

[0179] Fig. 160 shows the heat flux (ua) vs. temperature (°C) graphs of TPU samples with POSS-functionalized Nb nanoparticles, unprocessed and reprocessed, before and after 500h of UV aging and after 500h and 1000h of xenon aging.

[0180] Fig. 161 shows the E' graph at 23°C (MPa) of TPU samples and TPU with non-functionalized and APTES- and POSS-functionalized Nb nanoparticles, before and after 500h of UV aging and after 500h and 1000h of xenon aging.

[0181] Fig. 162 shows the Tg (°C) graph of TPU samples and TPU with non-functionalized and APTES- and POSS-functionalized Nb nanoparticles, before and after 500h of UV aging and after 500h and 1000h of xenon aging.

[0182] Fig. 163 shows the hardness graph (Shore A) of TPU and TPU samples with Nb nanoparticles, unfunctionalized and functionalized with APTES and POSS, before and after 500h of UV aging and after 1000h of xenon aging.

[0183] Fig. 164 shows the hardness graph (Shore A) of reprocessed TPU and TPU samples with Nb nanoparticles, unfunctionalized and functionalized with APTES and POSS, before and after 500h of UV aging and after 1000h of xenon aging.

[0184] Figure 165 shows the AVrel graph (mm 3 ) of TPU and TPU samples with Nb nanoparticles, unfunctionalized and functionalized with APTES and POSS, before and after 500h of UV aging and after 1000h of xenon aging.

[0185] Figure 166 shows the AVrel graph (mm 3) of reprocessed TPU and TPU samples with Nb nanoparticles, unfunctionalized and functionalized with APTES and POSS, before and after 500h of UV aging and after 1000h of xenon aging.

[0186] Fig. 167 shows the stress (MPa) vs. strain (%) graph of TPU and TPU samples with Nb nanoparticles, unfunctionalized and functionalized with APTES and POSS, before and after 500h of UV aging and after 1000h of xenon aging.

[0187] Fig. 168 shows the stress (MPa) vs. strain (%) graph of reprocessed TPU and Nb nanoparticle-coated TPU samples, both non-functionalized and functionalized with APTES and POSS, before and after 500h of UV aging and after 1000h of xenon aging.

[0188] Fig. 169 shows the tensile strength (MPa) graph of TPU and TPU samples with Nb nanoparticles, unfunctionalized and functionalized with APTES and POSS, before and after 500h of UV aging and after 1000h of xenon aging.

[0189] Fig. 170 shows the tensile strength (MPa) graph of reprocessed TPU and TPU samples with Nb nanoparticles, unfunctionalized and functionalized with APTES and POSS, before and after 500h of UV aging and after 1000h of xenon aging.

[0190] Fig. 171 shows the elongation at break (%) graph of TPU and TPU samples with Nb nanoparticles, unfunctionalized and functionalized with APTES and POSS, before and after 500h of UV aging and after 1000h of xenon aging.

[0191] Fig. 172 shows the elongation at break (%) graph of reprocessed TPU and TPU samples with Nb nanoparticles, unfunctionalized and functionalized with APTES and POSS, before and after 500h of UV aging and after 1000h of xenon aging.

[0192] Figure 173 shows the tear resistance graph (N / mm) of the TPU and TPU samples with Nb nanoparticles, non-functionalized and Functionalized with APTES and POSS, before and after 500h of UV aging and after 1000h of xenon aging.

[0193] Fig. 174 shows the tear resistance graph (N / mm) of reprocessed TPU and TPU samples with Nb nanoparticles, unfunctionalized and functionalized with APTES and POSS, before and after 500h of UV aging and after 1000h of xenon aging. Detailed Description of the Invention

[0194] The inventors developed a polymer composite with optimized properties, high efficiency, and improved cost-benefit ratio, using a metallic species and a polymeric matrix, incorporating a filler of metallic species particles into the polymeric matrix. Among the advantages provided are gains in hydrophobicity, weather and UV resistance, improved mechanical, thermal, and physicochemical properties; expanding applicability and added value. Furthermore, another advantage of the present invention is the ability to extend the lifespan of polymers and / or restore the properties of a recycled polymeric matrix to its virgin state.

[0195] In the context of the present invention, the term "metallic species" encompasses various metals, which may be in the form of oxides, hydrates, hydrides, carbides, nitrides, bonded to other metals or transition metals.

[0196] In the context of the present invention, the expression "Niobium species" encompasses various chemical entities containing Niobium, including metallic Niobium, oxides, hydrates, hydrides, carbides or nitrides of Niobium, iron Niobium or Niobium alloyed with other metals or transition metals, or combinations thereof. It also includes Niobium pentoxide (Nb2O5), Niobium dioxide (NbC3), Niobium oxide (NbO), Niobium oxalate, niobic acid and FeNb. It may be a mass quantity of microparticles, submicroparticles or nanoparticles.

[0197] In the context of the present invention, the expression "Tantalum species" It encompasses various chemical entities containing tantalum, including metallic tantalum, oxides, hydrates, hydrides, carbides or nitrides of tantalum, or tantalum bonded to other metals or transition metals, or combinations thereof. It also includes tantalum pentoxide (Ta2Os), tantalum dioxide (TaC), tantalum oxide (TaO). It can be a mass quantity of microparticles, submicroparticles or nanoparticles.

[0198] In the context of the present invention, the expression "titanium species" encompasses various chemical entities containing titanium, including metallic titanium, oxides, hydrates, hydrides, carbides or nitrides of titanium, or titanium alloyed with other metals or transition metals, or combinations thereof. It also includes titanium dioxide. This may be a mass quantity of microparticles, submicroparticles or nanoparticles.

[0199] In the context of the present invention, the expression "Hafnium species" encompasses various chemical entities containing Hafnium, including metallic Hafnium, oxides, hydrates, hydrides, carbides or nitrides of Hafnium, or Hafnium bonded to other metals or transition metals, or combinations thereof. It also includes Hafnium dioxide. This may be a mass quantity of microparticles, submicroparticles or nanoparticles.

[0200] In the context of the present invention, the expression "Zirconium species" encompasses various chemical entities containing Zirconium, including metallic Zirconium, oxides, hydrates, hydrides, carbides or nitrides of Zirconium, or Zirconium alloyed with other metals or transition metals, or combinations thereof. It also includes Zirconium dioxide and Zirconium monoxide. It may be a mass quantity of microparticles, submicroparticles or nanoparticles.

[0201] In the context of the present invention, the expression "Cerium species" encompasses various chemical entities containing Cerium, including metallic Cerium, oxides, hydrates, hydrides, carbides or nitrides of Cerium, or Cerium bonded to other metals or transition metals, or combinations thereof. It also includes Cerium dioxide and Cerium(III) oxide (Ce2Os). It may be a mass quantity of microparticles, submicroparticles or nanoparticles.

[0202] In the context of the present invention, the term "polymer matrix in its original or virgin state" refers to a non-recycled polymer matrix, obtained directly from polymer synthesis, without having been previously subjected to processing or utilization steps.

[0203] In the context of this invention, the term "recycled polymer matrix" refers to a polymer matrix that has already undergone at least one processing and / or use step.

[0204] In a first aspect, the present invention discloses a polymeric composite comprising: at least one polymeric matrix; and at least one filler of metallic particles, wherein said polymeric matrix comprises thermoplastic elastomer, thermoplastic polymer or combinations thereof, and wherein said metallic species comprises niobium, tantalum, titanium, hafnium, zirconium, cerium or combinations thereof.

[0205] In one embodiment of the polymer composite, the said polymer matrix is ​​TPU (thermoplastic polyurethane), PP (polypropylene), PU (polyurethane), PVC (polyvinyl chloride), ABS (acrylonitrile butadiene styrene), PA (polyamide), PEBAX (polyether block amide), PVDF (polyvinylidene fluoride), PET (polyethylene terephthalate), or combinations thereof.

[0206] In one embodiment, the aforementioned polymer matrix is ​​TPO (Thermoplastic Polyolefin).

[0207] In one embodiment of the polymer composite, the polymer matrix is ​​polypropylene or polyurethane. In another embodiment of the polymer composite, the polymer matrix is ​​recycled polypropylene or polyurethane.

[0208] In one embodiment of the polymer composite, the aforementioned metallic species is a type of niobium.

[0209] In one embodiment of the polymer composite, the aforementioned niobium species is niobium pentoxide.

[0210] In one embodiment of the polymer composite, the aforementioned species The metallic component comprises metallic nanoparticles in quantities ranging from 1 to 1000 ppm by mass of the composite.

[0211] In one embodiment of the polymer composite, the aforementioned metallic species comprises metallic nanoparticles in quantities ranging from 50 to 200 ppm by mass of the composite.

[0212] In one embodiment of the polymer composite, the aforementioned metallic species comprises metallic nanoparticles in quantities of 50, 100, and 200 ppm by mass of the composite.

[0213] In one embodiment of the polymeric composite, the aforementioned niobium species is functionalized with alkalizing species (e.g., AMP-95), chelating agents (e.g., citric acid, citrates, pyrophosphates, etc.), anhydrides (e.g., maleic anhydride, Bondyram, etc.), silanized species (e.g., APTES, Glycidyl-POSS, GPTMS, etc.), glycolic agents (e.g., polyethylene glycol of various sizes, butyl glycol, propanediol, etc.), hydrophobic agents using C18 fatty acids (e.g., oleic acid, stearic acid, etc.), hydrophobic silica crown (e.g., pyrogenic SiO2 + C18, etc.), phenyl esters of alkylsulfonic acid (e.g., mesamoll, etc.), metal oxides (e.g., aluminum hydroxide, etc.), or combinations thereof, among others.

[0214] In one embodiment, the niobium pentoxide nanoparticle load exhibits a significant degree of amortization.

[0215] In one embodiment, the nanoparticle load exhibits a degree of amortization of at least 19%.

[0216] In one embodiment, the said nanoparticle load preferably comprises a degree of amortization of at least 20%, more preferably at least 25%, more preferably at least 30%, more preferably at least 35%, more preferably at least 39%, more preferably at least 40%, more preferably at least 45%, more preferably at least 50%, more preferably a degree of amortization of at least 55%, more preferably at least 60%, more preferably at least 65%, and even more preferably a degree of crystallinity of at least 70%. In one embodiment, the degree Amortization of at least 71%, more preferably at least 72%, most preferably at least 73%. In a non-limiting embodiment, the amortization rate is 74%.

[0217] In one embodiment, the aforementioned nanoparticle load preferably comprises an amortization rate of at least 39%, preferably an amortization rate of at least 55%, and even more preferably an amortization rate of at least 70%.

[0218] In a second aspect, the present invention provides a method for modulating the properties of a polymeric matrix comprising at least one step of incorporating metallic particle filler into a polymeric matrix, wherein said polymeric matrix comprises thermoplastic elastomer, thermoplastic polymer or combinations thereof, and wherein said metallic species comprises niobium species, tantalum species, titanium species, hafnium species, zirconium species, cerium species or combinations thereof.

[0219] In one embodiment of the method, it aims to improve the mechanical, thermal, and physicochemical properties of a polymeric matrix.

[0220] In one embodiment of the method, the aforementioned polymer matrix is ​​in its recycled form.

[0221] In one embodiment of the polymer composite, the said polymer matrix is ​​TPU (thermoplastic polyurethane), PP (polypropylene), PU (polyurethane), PVC (polyvinyl chloride), ABS (acrylonitrile butadiene styrene), PA (polyamide), PEBAX (polyether block amide), PVDF (polyvinylidene fluoride), PET (polyethylene terephthalate), or combinations thereof.

[0222] In one embodiment, the aforementioned polymer matrix is ​​TPO (Thermoplastic Polyolefin).

[0223] In one embodiment of the polymer composite, the polymer matrix is ​​polypropylene or polyurethane. In another embodiment of the polymer composite, the polymer matrix is ​​recycled polypropylene or polyurethane.

[0224] In one embodiment of the method, the aforementioned incorporation step is preceded by a functionalization step of the metallic species with alkalizing species (e.g., AMP-95), chelating agents (e.g., citric acid, citrates, pyrophosphates, etc.), anhydrides (e.g., maleic anhydride, Bondyram, etc.), silanized species (e.g., APTES, Glycidyl-POSS, GPTMS, etc.), glycolic agents (e.g., polyethylene glycol of various sizes, butyl glycol, propanediol, etc.), hydrophobic agents using C18 fatty acids (e.g., oleic acid, stearic acid, etc.), hydrophobic silica crown (e.g., pyrogenic SiO2 + C18, etc.), phenyl esters of alkylsulfonic acid (e.g., mesamoll, etc.), metal oxides (e.g., aluminum hydroxide, etc.), or combinations thereof, among others.

[0225] In one embodiment of the method, the aforementioned metallic species is a type of niobium.

[0226] In one embodiment of the method, the aforementioned niobium species, niobium pentoxide, is incorporated at up to 1000 ppm.

[0227] In a third aspect, the present invention presents a use of the polymer composite as a structural, functional or finishing component.

[0228] In a concrete application of its use, the structural, functional, or finishing component is an automotive / vehicle part, a tool component, or a building material.

[0229] In a concrete application of its use, the structural, functional, or finishing component is an automotive / vehicle part.

[0230] In a concrete application of its use, the structural, functional, or finishing component is a tool component.

[0231] In a fourth aspect, the present invention provides for the use of metallic particles to restore the properties of a recycled polymer matrix to its virgin state, comprising at least one step of incorporating metallic particles into a recycled polymer matrix, wherein said polymer matrix comprises thermoplastic elastomer, thermoplastic polymer or combinations thereof. and wherein the said metallic species comprises niobium species, tantalum species, titanium species, hafnium species, zirconium species, cerium species, or combinations thereof.

[0232] In a concrete application, the aforementioned metallic species is a type of niobium.

[0233] In one specific application, the aforementioned polymer matrix is ​​made of recycled polypropylene or polyurethane.

[0234] The examples shown here are intended only to illustrate one of the numerous ways of carrying out the invention, without, however, limiting its scope. Example 1 - Modulation of dynamic-mechanical properties in PU resin

[0235] DMA (Dynamic Mechanical Analysis) tests were performed on polyurethane resin samples containing niobium pentoxide nanoparticles and AMP-95 neutralizer.

[0236] Niobium pentoxide nanoparticles were incorporated into PU resin (sample R86) at a concentration of 50 ppm, comparing standard resin, resin with nanoparticles, and resin with nanoparticles and AMP-95. The results for storage modulus (E') are shown in Figure 1.

[0237] Based on the results, it can be observed that, in samples without AMP-95, E' is more dependent on the concentration of nanoparticles. The addition of AMP-95 decreases this dependence, but causes the onset of E' to occur at lower temperatures.

[0238] Niobium pentoxide nanoparticles were incorporated into PU resin (sample R86) at a concentration of 100 ppm, comparing standard resin, resin with nanoparticles, and resin with nanoparticles and AMP-95. The results for storage modulus (E') are shown in Figure 2.

[0239] Based on the results, it can be observed that, in samples without AMP-95, E' is more dependent on the concentration of nanoparticles. The addition of AMP-95 decreases this dependence, but causes the onset of E' to occur at higher temperatures. lower.

[0240] Niobium pentoxide nanoparticles were incorporated into PU resin (sample R86) at a concentration of 200 ppm, comparing standard resin, resin with nanoparticles, and resin with nanoparticles and AMP-95. The results for storage modulus (E') are shown in Figure 3.

[0241] Based on the results, it can be observed that, in samples without AMP-95, E' is more dependent on the concentration of nanoparticles. The addition of AMP-95 decreases this dependence, but causes the onset of E' to occur at lower temperatures.

[0242] Niobium pentoxide nanoparticles were incorporated into PU resin (sample R86) at a concentration of 50 ppm, comparing standard resin, resin with nanoparticles, and resin with nanoparticles and AMP-95. The results for loss modulus (E”) are shown in Figure 4.

[0243] Based on the results, it can be observed that the addition of AMP-95 reduces the dependence of E” on the concentration of nanoparticles. For samples with AMP-95, the E” peak occurs at lower temperatures compared to the standard.

[0244] Niobium pentoxide nanoparticles were incorporated into PU resin (sample R86) at a concentration of 100 ppm, comparing standard resin, resin with nanoparticles, and resin with nanoparticles and AMP-95. The results for loss modulus (E”) are shown in Figure 5.

[0245] Based on the results, it can be observed that the addition of AMP-95 reduces the dependence of E” on the concentration of nanoparticles. For samples with AMP-95, the E” peak occurs at lower temperatures compared to the standard.

[0246] Niobium pentoxide nanoparticles were incorporated into PU resin (sample R86) at a concentration of 200 ppm, comparing standard resin, resin with nanoparticles, and resin with nanoparticles and AMP-95. The results for loss modulus (E”) are shown in Figure 6.

[0247] Based on the results, it can be observed that the addition of AMP-95 reduces the The dependence of E” on the concentration of nanoparticles. For samples with AMP-95, the E” peak occurs at lower temperatures compared to the standard.

[0248] Niobium pentoxide nanoparticles were incorporated into PU resin (sample R86) at a concentration of 50 ppm, comparing standard resin, resin with nanoparticles, and resin with nanoparticles and AMP-95. The results for damping factor (Tan õ) are shown in Figure 7.

[0249] Based on the results, it is possible to observe that the Tg curves follow the trend observed previously. Increasing the concentration of nanoparticles decreases Tg. The addition of AMP-95 reduces the dependence of Tg on the concentration of nanoparticles.

[0250] Niobium pentoxide nanoparticles were incorporated into PU resin (sample R86) at a concentration of 100 ppm, comparing standard resin, resin with nanoparticles, and resin with nanoparticles and AMP-95. The results for damping factor (Tan õ) are shown in Figure 8.

[0251] Based on the results, it is possible to observe that the Tg curves follow the trend observed previously. Increasing the concentration of nanoparticles decreases Tg. The addition of AMP-95 reduces the dependence of Tg on the concentration of nanoparticles.

[0252] Niobium pentoxide nanoparticles were incorporated into PU resin (sample R86) at a concentration of 200 ppm, comparing standard resin, resin with nanoparticles, and resin with nanoparticles and AMP-95. The results for damping factor (Tan õ) are shown in Figure 9.

[0253] Based on the results, it is possible to observe that the Tg curves follow the trend observed previously. Increasing the concentration of nanoparticles decreases Tg. The addition of AMP-95 reduces the dependence of Tg on the concentration of nanoparticles.

[0254] It can be concluded from the results above that increasing the concentration of nanoparticles leads to a decrease in the peak temperature of E” and Tg. The addition of AMP-95 increases the stability of the dynamic properties. Mechanical effects decrease the dependence of these effects on nanoparticle concentration. It can be assumed that the effect of AMP-95 is more beneficial for concentrations of 200 ppm or higher.

[0255] Niobium pentoxide nanoparticles were incorporated into PU resin (sample R92) at concentrations of 50 ppm, 100 ppm, and 200 ppm compared to the standard resin, with the nanoparticles functionalized with AMP-95. The results for storage modulus (E') are shown in Figure 10.

[0256] The results show that the addition of functionalized nanoparticles reduces the stiffness of the polymer matrix. As the concentration of nanoparticles increases, E' decreases. At 200 ppm, the E' curve is similar to that of the standard sample, indicating a possible inflection point.

[0257] Niobium pentoxide nanoparticles were incorporated into PU resin (sample R92) at concentrations of 50 ppm, 100 ppm, and 200 ppm compared to the standard resin, with the nanoparticles functionalized with AMP-95. The results for loss modulus (E”) are shown in Figure 11.

[0258] There appears to be no linear dependence between nanoparticle concentration and energy dissipation. The highest E” peak is observed at a concentration of 200 ppm.

[0259] Niobium pentoxide nanoparticles were incorporated into PU resin (sample R92) at concentrations of 50 ppm, 100 ppm, and 200 ppm compared to the standard resin, with the nanoparticles functionalized with AMP-95. The results for the damping factor (Tan õ) are shown in Figure 12.

[0260] At all concentrations tested, the observed Tg is around -30°C. The Tg peak is slightly shifted to higher temperatures at 200 ppm. The addition of nanoparticles appears to favor energy dissipation.

[0261] Based on the results above, it can be concluded that there appears to be competition between the effects of nanoparticle concentration and AMP functionalization. Up to 100 ppm, the addition of functionalized nanoNb reduces E' and tanD. On the other hand, there appears to be an inflection point at 200 ppm. The addition of functionalized nanoparticles enhances the energy dissipation capacity above Tg in R92 samples, particularly at 200 ppm. Example 2 - Process for obtaining TPU and characterizing samples

[0262] To obtain TPU samples, niobium pentoxide nanoparticles functionalized with APTES and Glycidyl-POSS were used.

[0263] A simplified flowchart of the process for obtaining nanoparticles functionalized with APTES can be seen in Figure 13. A simplified flowchart of the process for obtaining nanoparticles functionalized with Glycidyl-POSS can be seen in Figure 14.

[0264] To characterize the produced masterbatches, TGA and DSC analyses were performed. The TGA results are summarized in Table 1 below:

[0266] The DSC results are summarized in Table 2 below:

[0267] Table 2 - DSC Results

[0268] Masterbatch options were tested as described in Table 3:

[0269] Table 3 - Masterbatch options Screws with one mixing zone and screws with two mixing zones under the following parameters set out in Table 4 below.

[0271] Table 4 - Extrusion parameters

[0272] The following pressure and torque parameters were used for samples with 50, 200, and 800 ppm of nanoparticles in a screw extruder with two mixing zones, as shown in Table 5 below.

[0273] Table 5 - Parameters in a screw extruder with two mixing zones.

[0274] For the TPU nanoparticle injection molding process, the following parameters were considered, as shown in Table 6 below. Example 3 - DMA dimensional evaluation results of the TPU samples obtained

[0276] The dimensional evaluation results for the TPU samples obtained are shown in Table 7 below.

[0277] Table 7 - Results of the dimensional assessment *Regarding the injection mold measurements

[0278] Next, DMA tests were performed on the TPU samples.

[0279] Figure 15 shows the storage module results for TPU + nanoparticle samples compared to virgin TPU (obtained at 1 Hz).

[0280] Figure 16 shows the loss modulus results for the TPU + nanoparticle samples compared to virgin TPU (obtained at 1 Hz).

[0281] Figure 17 shows the damping factor results for TPU + nanoparticle samples compared to virgin TPU (obtained at 1 Hz).

[0282] Figure 18 shows the storage module results for TPU samples + APTES-functionalized nanoparticles compared to virgin TPU (obtained at 1 Hz).

[0283] Figure 19 shows the loss modulus results for TPU samples with APTES-functionalized nanoparticles compared to virgin TPU (obtained at 1 Hz).

[0284] Figure 20 shows the damping factor results for TPU samples with APTES-functionalized nanoparticles compared to virgin TPU (obtained at 1 Hz).

[0285] Figure 21 shows the storage module results for TPU samples + Glycidyl-POSS functionalized nanoparticles compared to virgin TPU (obtained at 1 Hz).

[0286] Figure 22 shows the loss modulus results for TPU samples with Glycidyl-POSS functionalized nanoparticles compared to virgin TPU (obtained at 1 Hz).

[0287] Figure 23 shows the damping factor results for TPU samples with Glycidyl-POSS functionalized nanoparticles compared to virgin TPU (obtained at 1 Hz).

[0288] The results of the DMA analysis are summarized in Table 8 below.

[0289] Table 8 - DMA analysis results Example 3 - DSC characterization and tensile strength of TPU samples

[0290] To evaluate the effect of nanoparticles, DSC extrusion and injection molding tests were performed with TPU samples without nanoparticles, with 50, 200, and 800 ppm of niobium nanoparticles, and with 50, 200, and 800 ppm of niobium nanoparticles functionalized with different functional groups. The results of this characterization are described in Figures 24 to 34 and Table 9.

[0291] Table 9 - Tg (°C) results; comparison of TPU samples after extrusion and injection. Example 4 - TGA characterization and mechanical testing of TPU samples

[0292] The characterization results are described in Figures 35 to 48 and Tables 10 and 11. In Figures 35 to 46, it can be observed that, for the mass (%) x temperature (°C) graphs, the 1 o The degradation stage (rigid phase) occurs between approximately 250°C-320°C, while the 2o The degradation stage (flexible phase) occurs between approximately 320°C and 420°C. For the DTG (% / °C) vs. temperature (°C) graphs, the 1 o This stage occurs between approximately 210°C-310°C, and the 2nd o This stage occurs between approximately 310°C-420°C. An increasing trend in degradation temperature is also observed when nanoparticles (functionalized or non-functionalized) are added to TPU. This trend occurs for both injection molding and extrusion, but more markedly for extrusion.

[0293] Table 10 - Comparison of DTG (°C) results of TPU samples after extrusion and injection.

[0294] Figure 47 shows that the addition of niobium nanoparticles contributes to improving the hardness of TPU. This behavior can be attributed to the interaction between the polymer matrix and the nanoparticles, which can act as reinforcements, improving the material's rigidity. Regardless of whether they were functionalized or not, the nanoparticles increased the hardness value by 0.25 to 1.2% compared to the standard.

[0295] Regarding abrasion, Table 11 indicates that the addition of nanoparticles Non-functionalized niobium (TPU / Nb) showed little significant effect on abrasion resistance.

[0296] Functionalization with APTES also showed more varied results, indicating less wear at the 200 ppm concentration.

[0297] ■ Functionalization with POSS showed promise at intermediate concentrations (200 ppm), resulting in a composite with improved wear resistance performance (pure TPU).

[0298] Table 11 - Abrasion test results (ISO 4649)

[0299] Figure 48, relating to tear resistance (ASTM D624), shows that, regardless of the nanoparticle functionalization process, nanocomposites formed with a nanoparticle concentration of 200 ppm tend to exhibit greater tear resistance. The nanocomposite formed with a concentration of non-functionalized nanoparticles of 800 ppm proved to be less resistant to tearing, mainly in relation to the other nanocomposites with non-functionalized nanoparticles and TPU.

[0300] Additionally, the possible causes of the peaks observed in the DSC are discussed: Recrystallization of rigid segments - When heated, part of these regions can reorganize to form more stable crystals (nanoparticles may influence this); Reorganization of hydrogen bonds - Reorganization of rigid and flexible phases, especially in the rigid ones. Nanoparticles can act as nucleating agents or interfere with the interactions between the Phases. The presence of nanoparticles can increase the number and dimensions of rigid domains in TPU; Delayed crosslinking processes - Crosslinking of urethane groups and free ureas. Example 5 - Activation Energy (Flynn-Wall-Ozawa-FWO Method)

[0301] The activation energy (Ea) of a given reaction can be calculated using the FWO isoconversional method from mass loss data as a function of temperature, or enthalpy of a given chemical reaction, obtained at different heating rates, using the following equation:

[0302] Equation 1: log( ) = log(^) - log ( 2.315 - 0.4567^

[0303] Where: g (a(T)) is a relation as a function of conversion, Ea is the activation energy, R is the gas constant, A is a pre-exponential factor, is the heating rate, and T is the absolute temperature.

[0304] The isoconversional method is an approach used in thermal kinetics to determine the activation energy of a reaction without assuming a specific model. It is based on the principle that, for the same degree of conversion (a), the reaction rate can be analyzed at different temperatures to obtain information about the kinetic parameters.

[0305] For different heating rates (5, 10, 20 and 40 °C / min) 1 ), at a given conversion to, a linear relationship is observed through a log graph ( <P) versus MT, e a energia aparente de ativação (Ea) é obtida a partir da inclinação do ajuste linear, segundo a equação a seguir:

[0306] Equation 2: y = ax + b

[0307] Where: y = log ( ) b = log (A.Ea / R) - log (g(a(T))) - 2.315 a = 0.4567. Ea / R x = - 1 / T

[0308] The results of such analyses are described in figures 49 to 53. In figure 53, the rigid phase begins at approximately 0.05 of the conversion, up to approximately 0.16; and the flexible phase begins at approximately 0.19 up to approximately 0.3. Example 6 - Creep characterization and characterization of reprocessed materials

[0309] The results of the creep characterization at 30°C are shown in Figures 54 and 55. The results of the characterization of the reprocessed materials (DMA) are shown in Figures 56 to 70.

[0310] Based on these results, it can be observed that all reprocessed samples showed greater abrasion loss compared to non-reprocessed references, and the reprocessed samples containing nanoparticles showed less abrasion loss compared to pure TPU. TPU / NbAPTES showed the lowest loss among the samples analyzed.

[0311] Regarding hardness, there was no significant variation in the hardness of pure TPU; however, the samples with Nb, Nb-APTES, and Nb-POSS showed similar behavior, with a tendency towards a reduction in hardness.

[0312] The TPU and TPU Nb samples showed significant losses in mechanical strength after reprocessing, while the TPU Nb-APTES and TPU Nb-POSS samples retained this property. These two samples also showed greater elongation at break.

[0313] All reprocessed samples showed lower average values ​​compared to non-reprocessed references. However, TPU Nb-APTES did not show a significant difference.

[0314] The colorimetry of the xenon-aged samples (figures 69 and 70) was analyzed using the CIELAB color parameters = L', a', b'. Example 7 - FTIR, TGA and DSC characterization of reprocessed materials and characterization of materials aged in Xenon for 500h

[0315] Figures 71-74 show the FTIR spectra of the analyzed samples. The wavenumbers (cm' 1 The values ​​corresponding to different connections are indicated in Table 12 below.

[0316] Table 12 - Connections and their corresponding wavenumbers in an FTIR analysis

[0317] Figures 75-78 show the results of the TGA analyses of the samples.

[0318] For the three TPU processing methods, no alterations or formation of different compounds were observed. The spectra showed the same profiles, highlighting the main characteristic peaks of TPU.

[0319] In samples containing nanoparticles, the characteristic stretching peak of the Nb-O-Nb bond was at 843 cm⁻¹. -1 It appears to be obscured, possibly due to overlapping with the absorption peaks of the TPU matrix.

[0320] The peak at 2361 cm 1 It is characteristic of CO2, specifically related to its asymmetric stretching vibration, which may be adsorbed onto the nanoparticle.

[0321] In the TPU / NbAPTES and TPU / NbPOSS samples, it is not possible to visualize the characteristic peak of Si-O-Si bonds (1129 cm⁻¹). 1 ), originating from the functionalizing agents, possibly due to the overlapping of the absorption peaks of the TPU matrix.

[0322] No significant difference was observed between the thermal degradation of TPUs after the first and third processing. Deconvolution of the 3P curves was performed to confirm the TPU degradation peaks.

[0323] The degradation profile of the TPU / POSS sample showed slight differences after the third processing. It can be observed that there is a shift of the second peak (referring to the flexible phase) to lower temperatures when the TPU / POSS underwent reprocessing. This difference is more clearly visible in the deconvolution of the 3P sample, as it shows 2 peaks in the second degradation related to the flexible phase, unlike the other samples which show 3 peaks.

[0324] Figures 79-82 show the results of the DSC analyses of the samples.

[0325] A small temperature peak of around 150°C was observed during the first heating in 1P, which may be related to the reorganization of hydrogen bonds between the rigid and flexible phases, especially in the rigid phases. In the second heating, the samples showed similar thermal behavior. It is observed that the samples exhibited similar thermal behavior.

[0326] During the first heating, a small temperature peak of around 150°C was observed in the 3P sample, which may be related to the reorganization of hydrogen bonds between the rigid and flexible phases, especially in the rigid phases. In the second heating, the samples exhibited similar thermal behaviors.

[0327] Table 13 below shows a comparison of the Tg values ​​obtained. From the Tg values ​​obtained for the reprocessed samples, it is possible to observe a small temperature change between the processing cycles, but these changes are not representative.

[0328] Table 13 - Reprocessing Characterization Results

[0329] Figures 83-86 show FTIR spectra after 500h of xenon aging of the reprocessed and non-reprocessed samples.

[0330] Absorption in the region above 3500 cm² 1 This indicates the presence of OH originating from the hydrolysis of TPU Polyester. Furthermore, changes in the 3330 cm⁻¹ peaks are observed. 1 and 1727 cm 1 The molecules corresponding to the NH and C=O groups indicate the breaking of bonds and the formation of new compounds, and may indicate oxidation.

[0331] Figure 87 indicates that TPU hydrolysis occurs primarily in the flexible phase, through the breakdown of the polyester. The activation energy of TPU-NbPOSS shows a significant drop when it undergoes degradation of the flexible phase.

[0332] Finally, Figure 88 shows the effect of xenon aging, at different times, on the E' (23°C) and Tg of the samples. Example 8 - Characterization of materials aged in xenon for 500h and 1000h

[0333] Figures 89-104 show the TGA results of the samples, while Table 14 shows a comparison of the results before and after aging.

[0334] Table 14 - Comparison of DTG results before and after 500h of xenon aging.

[0335] The TPU sample, after 500 hours of aging, did not show a decrease in degradation temperatures. Considering the DTG thermograms, it is possible to assess that only a variation in the intensity of the maximum degradation peaks occurred. The TPU-R samples also showed very similar behavior, even after 500 hours of aging. Considering the DTG thermograms, it is possible to assess that a slight decrease in the intensity of the maximum degradation peaks occurred.

[0336] The TPU / Nb sample, after 500 hours of aging, showed an 11°C increase in the maximum degradation peak for the flexible phase, indicating a trend towards improved thermal properties. The TPU / Nb-R sample also showed a trend towards improved thermal properties, with a 7°C increase in the degradation temperature.

[0337] The TPU / NbAPTES samples, after 500 hours of aging, showed an increase in degradation temperature of 9°C at the peak corresponding to the flexible phase. The TPU / NbAPTES-R sample also showed a tendency for an increase in degradation temperature after aging of 16°C in the flexible phase.

[0338] The TPU / NbPOSS sample, after 500 hours of aging, showed the opposite behavior to the others, exhibiting a decrease in the degradation temperature of 9 °C at the peak corresponding to the flexible phase. The TPU / NbPOSS-R sample, however, showed a tendency for an increase in the degradation temperature after aging, of 16 °C in the flexible phase.

[0339] Table 15 below shows the DSC results for the samples. It can be observed that the samples after 500h of aging in Xenon showed a tendency for Tg to decrease, however the sample with the greatest variation in Tg was the TPU / POSS sample, which corroborates the behavior evaluated in the TGA analysis.

[0340] Table 15 - Comparison of Tg (°C) of TPU samples before and after 500h of xenon aging.

[0341] Figures 105-118 show the results of the material characterization after 1000h of xenon aging.

[0342] A decrease in hardness was observed after aging in both reference and reprocessed samples. Hardness was a property that was little affected (maximum loss of 10% - TPU-R) and appears to be preserved in samples with Nb, especially after reprocessing.

[0343] There was a decrease in tensile strength at break in all samples after aging. In the reference samples, the difference after aging was significant (28 to 37% loss). For the reprocessed samples, TPU with functionalized Nb nanoparticles showed greater preservation of the property. There was a 67% loss in the TPU-R and TPU Nb-R samples, while TPU APTES-R and TPU POSS-R had losses of 49% and 42%, respectively.

[0344] Only the TPU / NbAPTES sample showed a slight increase in elongation at break after aging. All reprocessed samples subjected to aging showed a reduction in elongation at break.

[0345] Only the reference TPU / NbAPTES sample showed an increase in tear resistance after aging. There was a considerable loss in tear resistance for reprocessed samples (28% for TPU-R, 32% for Nb-R and 37.5% for APTES-R). The reprocessed sample, with Nb functionalized with POSS, had better retention of the property (loss of only 15.2%).

[0346] All samples showed considerable losses in abrasion resistance after 1000 h of aging. The reprocessed TPU sample exhibited the greatest loss of abrasion resistance, while the reprocessed samples containing nanoparticles showed greater resistance compared to TPU-R. Example 8 - FTIR, TGA and DSC characterization of reprocessed materials and characterization of materials aged in Xenon for 1000h

[0347] Figures 119-122 show FTIR spectra comparing samples before and after 500h and 1000h with xenon. For samples without the addition of nanoparticles, small changes can be observed in the 3330 cm⁻¹ peaks. -1 and 1727 cm -1 The bands corresponding to the NH and C=O groups may indicate bond breaking and the formation of new compounds. The broadening of the C=O band and changes in the regions corresponding to CN and C-O bonds indicate oxidation of the material. A large peak can be observed at 3500 cm⁻¹. -1 This indicates the presence of OH originating from the hydrolysis of TPU, which occurs mainly in the flexible phase due to the breakdown of the polyester. However, in the TPU sample at 1000h, this peak decreases, and in TPU-R it also decreases compared to the samples at 500h.

[0348] For samples with Nb nanoparticles, a broad peak can be observed at 3500 cm⁻¹, indicating the presence of OH originating from the hydrolysis of TPU, which occurs mainly in the flexible phase due to polyester breakdown. In the TPU / Nb samples, after 1000h of aging, hydrolysis was observed, unlike what was observed at 500h. In the reprocessed samples, a slight decrease in the peak occurred, but hydrolysis was still present at both 500h and 1000h.

[0349] For samples with APTES-functionalized Nb nanoparticles, a broad peak can be observed at 3500 cm⁻¹, indicating the presence of OH originating from TPU hydrolysis, which occurs mainly in Flexible phase, due to polyester breakdown. In samples containing APTES, hydrolysis was only observed in reprocessed samples.

[0350] Of all the samples evaluated, the samples with Nb / POSS, both the reference samples and those reprocessed after 1000h of aging, did not show peak broadening at 3500 cm⁻¹. The TPU / NbPOSS sample showed hydrolysis at 500h, but after 1000h it no longer showed hydrolysis. This may indicate that hydrolysis occurs during aging, followed by reconfiguration and stabilization.

[0351] Figures 123-130 show the results of the DSC analysis of the samples, while Table 16 shows a comparison between the T g (°C) of the samples before aging and aged for 500h and 1000h by xenon.

[0352] Table 16

[0353] The TPU sample, after 500 hours of aging, showed a decrease of 7.25 °C in temperature. g The TPU-R sample, after 500 hours of aging, showed a decrease of 2.83 °C in its temperature. g In 1000 hours of aging, there is a slight increase in T gThe difference between the TPU and TPU-R samples, however, is not significant enough to suggest a trend.

[0354] The TPU / Nb sample, after 500 hours of aging, showed a decrease of 6.64 °C in temperature. g The TPU / Nb-R sample, after 500 hours of aging, showed a decrease of 5.72 °C in temperature. g The TPU / Nb sample, after 1000 hours of aging, showed temperature stability. g , and the TPU / Nb ratio showed a decrease of less than 1°C, which also indicates stability.

[0355] The TPU / NbAPTES sample, after 500 hours of aging, showed a decrease of 6.93 °C in temperature. g The TPU / NbAPTES-R sample, after 500 hours of aging, showed a decrease of 7.22 °C in temperature. g The TPU / NbAPTES and TPU / NbAPTES-R samples, after 1000 hours of aging, showed stability at the temperature. g with respect to samples after 500 hours of aging.

[0356] The TPU / NbPOSS sample, after 500 hours of aging, showed a decrease of 9.47 °C in temperature. g The TPU / NbPOSS sample, after 1000 hours of aging, showed a decrease of approximately 2°C compared to the T sample. g After 500 hours of aging, the sample can be considered stable after 500 hours of aging, since, as seen in the FTIR analysis, this sample shows hydrolysis after 500 hours, but no longer shows it after 1000 hours.

[0357] The TPU / NbPOSS-R samples, after 500 hours of aging, showed a decrease of 6.65 °C in temperature. g However, after 1000 hours, there was no significant change compared to 500 hours of aging. The samples after 1000 hours of aging in Xenon showed a tendency towards stability of the T g with regard to T g s of the samples after 500h.

[0358] Figures 131-136 show the DMA results of the aged samples. An increase in stiffness is observed in all reference samples after xenon aging. For the reprocessed samples, after 500h aging the modulus increases, indicating possible crosslinking and / or reassociation of molecular segments. However, after 1000h the modulus is preserved for the samples containing APTES and POSS, indicating greater resistance to degradation.

[0359] An increase in stiffness was also observed at temperatures of -40°C, -10°C, and 23°C for all samples after xenon aging. No significant difference in stiffness at -40°C was observed for the TPU / NbAPTES sample. There is no significant difference in stiffness values ​​above the second glass transition temperature (T g (of the rigid segment).

[0360] No significant influence of xenon aging on the glass transition temperature of the flexible segment of the non-reprocessed samples was observed. Reprocessed samples containing APTES and POSS, aged for 1000h, proved to be less susceptible to aging.

[0361] The variation in length was very low for all samples after aging, while the variation in width was lower for TPU with NbAPTES and NbPOSS. For reprocessed materials, the smallest variation was observed in TPU-R and TPU / NbPOSS-R. Example 9 - FTIR, TGA and DSC characterization of reprocessed materials and characterization of materials aged in UV

[0362] Figures 137-144 show the comparative FTIR spectrum of samples aged for 500h by UV and different times by xenon.

[0363] For samples without the addition of nanoparticles, small changes can be observed in the 3330 cm⁻¹ peaks. 1 and 1727 cm 1corresponding to the NH and C=O groups, which may indicate bond breaking and the formation of new compounds. A broad peak can also be observed at 3500 cm⁻¹. 1 , which indicates the presence of OH resulting from photo-oxidation in UV aging and from the combination of photo-oxidation and TPU hydrolysis.

[0364] For samples with the addition of non-functionalized nanoparticles, a broad peak can be observed at 3500 cm⁻¹. 1 This indicates the presence of OH resulting from photo-oxidation during UV aging (500h) and from the combination of photo-oxidation and TPU hydrolysis (1000h) in the reference samples. In the reprocessed samples, the peak corresponding to OH can be visualized in all samples.

[0365] For samples with added APTES-functionalized nanoparticles, a broad peak can be observed at 3500 cm⁻¹. 1, which indicates the presence of OH resulting from photo-oxidation during UV aging (500h) in the reference samples. In the reprocessed samples, it is possible to visualize the peak corresponding to OH in all samples.

[0366] For samples with the addition of POSS-functionalized nanoparticles, a broad peak can be observed at 3500 cm⁻¹. 1 , which indicates the presence of -OH originating from photo-oxidation in UV aging (500h) and from the combination of photo-oxidation and TPU hydrolysis (1000h) in the reference samples. In the reprocessed samples, it is possible to visualize the peak corresponding to -OH originating from photo-oxidation only in UV aging (500h).

[0367] Figures 145-152, as well as Table 17, show the results of the TGA analyses of the aged samples.

[0368] Table 17 - Comparison of TGA results of samples aged for 500h by UV and for different times by xenon.

[0369] For samples without added nanoparticles, the TPU and TPU-R samples, after 500 hours of UV and Xenon aging, did not show a significant decrease in degradation temperatures. However, after 1000 hours of Xenon aging, a decrease of 16 °C was observed for TPU and 20 °C for TPU-R in the flexible phase.

[0370] The TPU / Nb sample after UV and Xenon aging did not show a significant decrease in degradation temperatures. However, in the TPU / Nb-R sample after 500h of UV aging and 1000h of Xenon aging, a 15 °C decrease in the degradation temperature in the flexible phase was observed.

[0371] The TPU / NbAPTES sample, after 500 hours of UV and Xenon aging, did not show a significant decrease in degradation temperatures, while after 1000 hours of Xenon aging, it showed an increase of 23°C. However, in the TPU / NbAPTES-R sample, after UV and Xenon aging, an increase in the degradation temperature in the flexible phase can be observed.

[0372] The TPU / NbPOSS sample, after 500h and 1000h of Xenon aging, showed a slight decrease in degradation temperatures. However, in the TPU / NbPOSS-R sample, after 500h and 1000h of Xenon aging, an increase in the degradation temperature in the flexible phase can be observed.

[0373] After 500h UV aging and 500h and 1000h Xenon aging, in general, the samples containing nanoparticles, including the reprocessed ones, maintained or showed a shift in degradation peaks to higher temperatures.

[0374] Figures 153-160, as well as Table 18, show the results of the DSC analyses of the aged samples.

[0375] Table 18 - Comparison between the results of T g of samples aged for 500 hours by UV and for different times by xenon

[0376] For samples without added nanoparticles, after 500 hours of UV aging and 500 and 1000 hours of xenon aging, there is a decrease in Tg compared to unaged samples. However, in xenon aging, there is no significant change in Tg between 500 and 1000 hours. 1000h.

[0377] For samples with added non-functionalized nanoparticles, after 500h of UV aging and 500h and 1000h of xenon aging, there is a decrease in Tg compared to unaged samples. However, in xenon aging, there is no significant change in Tg between 500 and 1000h.

[0378] For samples with added APTES-functionalized nanoparticles, after 500h of UV aging and 500h and 1000h of xenon aging, there is a decrease in Tg compared to unaged samples. However, in xenon aging, there is no significant change in Tg between 500 and 1000h.

[0379] For samples with added POSS-functionalized nanoparticles, after 500h of UV aging and 500h and 1000h of xenon aging, there is a decrease in Tg compared to unaged samples. However, in xenon aging, there is no significant change in Tg between 500h and 1000h.

[0380] The decrease in Tg is attributed to the photo-oxidation process of TPU, which causes polymer chain breakage and increased chain mobility – consequently reducing Tg. However, when comparing Tg values ​​between 500 h and 1000 h (Xenon) of exposure to xenon radiation, there are no significant variations, suggesting that the most intense degradation occurs in the first 500 h of exposure. After this period, the material can reach a state of relative thermal stability, with a lower rate of further degradation.

[0381] Figures 161-174 show the DMA characterization results of the aged samples.

[0382] Increased stiffness was observed after UV aging in the TPU / Nb and TPU / NbAPTES samples. No significant difference was observed in Tg after UV aging.

[0383] There was a decrease in hardness after UV aging in the samples. Reference and reprocessed samples. This property was little affected by UV degradation, with a maximum loss of 10%. There are no significant differences between the samples - the variation between them was less than 3%.

[0384] An increase in the volume removed by abrasion occurred after UV aging for all samples. TPU was the least affected by UV among the reference samples. TPU / NbPOSS-R was the least affected by UV among the reprocessed samples.

[0385] Aging significantly altered the tensile behavior of the materials. The impact was greater for reprocessed materials that had been aged in Xenon.

[0386] There was a decrease in tensile strength in all samples after 500 hours of UV aging. There is no significant difference between the values ​​of the samples aged by UV (~20 - 23 MPa).

[0387] All samples showed increased elongation at break after 500 hours of UV aging. UV degradation can disrupt rigid domains and crystalline regions, potentially leading to greater flexibility and reduced strength. The TPU / NbAPTES-R sample exhibited the greatest elongation after aging.

[0388] All samples showed either preservation or slight reduction in tear resistance after UV treatment. Among the reprocessed samples, TPU / NbAPTES-R showed the best preservation of tear resistance.

[0389] Finally, the results of the colorimetry analyses are shown in Table 19 below.

[0390] Table 19 - Comparative results of the colorimetry analysis of the aged samples.

[0391] There was a decrease in the L' parameter for all samples, meaning that darkening occurred. There was also an increase in the a' parameter for all samples, indicating a greater red tone, as well as an increase in the b' parameter for all samples, indicating yellowing.

[0392] The samples with the greatest color variations were those containing non-functionalized nanoparticles, while the sample with the smallest color variations was TPU / NbAPTES.

[0393] Those skilled in the art will appreciate the knowledge presented here and will be able to reproduce the invention in the forms presented and in other variants and alternatives, covered by the scope of the following claims.

Claims

Claims 1. Polymer composite characterized by comprising: - at least one polymeric matrix; and - at least one charge of metallic particles, wherein said polymeric matrix comprises thermoplastic elastomer, thermoplastic polymer or combinations thereof, and wherein said metallic species comprises niobium, tantalum, titanium, hafnium, zirconium, cerium or combinations thereof.

2. Polymer composite according to claim 1 characterized in that said polymer matrix is ​​of TPU (thermoplastic polyurethane), PP (polypropylene), PU (polyurethane), PVC (polyvinyl chloride), ABS (acrylonitrile butadiene styrene), PA (polyamide), PEBAX (polyether block amide), PVDF (polyvinylidene fluoride), PET (polyethylene terephthalate) or combinations thereof.

3. Polymer composite according to claim 2 characterized in that said polymer matrix is ​​made of polypropylene or polyurethane.

4. Polymer composite according to claim 3 characterized in that said polymer matrix is ​​made of recycled polypropylene or polyurethane.

5. Polymer composite according to claim 1 characterized in that said metallic species is a Niobium species.

6. Polymer composite according to claim 5 characterized in that said niobium species is niobium pentoxide.

7. Polymer composite according to claim 1 characterized by said filler of metallic particles comprising metallic nanoparticles in an amount of 1 to 1000 ppm by mass of the composite.

8. Polymer composite according to claim 5 characterized in that said niobium species is functionalized with alkalizing, chelating, anhydride, silanized, glycolic, hydrophobic species using fatty acids, hydrophobic silica crown, phenyl esters of alkylsulfonic acid, metal oxides or combinations thereof.

9. A method for modulating the properties of a polymeric matrix, characterized by comprising at least one step of incorporating metallic particle fillers into a polymeric matrix, wherein said polymeric matrix comprises a thermoplastic elastomer, a thermoplastic polymer, or combinations thereof, and wherein said metallic species comprises a niobium species, a tantalum species, a titanium species, a hafnium species, a zirconium species, a cerium species, or combinations thereof.

10. Method according to claim 9, characterized in that the polymer matrix is ​​in its recycled form.

11. Method according to claim 9 or 10, characterized in that said incorporation step is preceded by a functionalization step of the metallic species with alkalizing, chelating, anhydride, silanized, glycolic, hydrophobic species using fatty acids, hydrophobic silica crown, phenyl esters of alkylsulfonic acid, metal oxides or combinations thereof.

12. Use of the polymer composite, as defined in claim 1, characterized by being used as a structural, functional or finishing component.

13. Use of metallic particles, characterized by being used to return the properties of a recycled polymeric matrix to its virgin state, comprising at least one step of incorporating metallic particles into a recycled polymeric matrix, wherein said polymeric matrix comprises thermoplastic elastomer, thermoplastic polymer or combinations thereof, and wherein said metallic species comprises niobium, tantalum, titanium, hafnium, zirconium, cerium or combinations thereof.

14. Use according to claim 13 characterized in that said niobium species is niobium pentoxide.

15. Use according to claim 13 characterized in that said polymer matrix is ​​made of recycled polypropylene or polyurethane.

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