Waterborne polyurethane-urea dispersions (WPUD), which are based on 100% bio-based semi-crystalline polyester polyol and isophorone diisocyanate, have been successfully synthesized and doped with single-walled carbon nanotubes (SWCNT) to obtain a finishing agent that provides textiles with multifunctional properties. The chemical structure of WPUD has been characterized by Fourier-transform infrared spectroscopy (FTIR) and nuclear magnetic resonance (NMR). The thermal properties have been evaluated by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and dynamic mechanical thermal analysis (DMTA). Mechanical properties have been studied by tensile stress–strain analysis. Moreover, the particle size, particle size distribution (PSD), and stability of developed waterborne dispersions have been assessed by dynamic light scattering (DLS), Z-potential, and accelerated aging tests (analytical centrifugation). Subsequently, selected fabrics have been face-coated by the WPUD using knife coating method and their properties have been assessed by measuring water contact angle (WCA), water column, fabric stiffness, and air permeability. The electrical conductivity of textiles coated with SWCNT-doped WPUD has been evaluated by EN 1149 standard. Finally, the surface morphologies of uncoated and coated fabrics have been studied by scanning electron microscopy (SEM). All of the synthesized polyurethane-ureas provide the coated substrates with remarkable water-repellency and water column, being therefore a more sustainable alternative to waterproof coatings based on fluoropolymers, such as PTFE. The additivation of the polymeric matrices with SWCNT has led to textile coatings with excellent electrical conductivity, maintaining water column properties, giving rise to multifunctional coatings that are highly demanded in protective workwear and technical textiles.

Waterborne polyurethane-urea dispersions (WPUD), which are based on fully biobased amorphous polyester polyol and isophorone diisocyanate (IPDI), have been successfully synthesized obtaining a finishing agent that provides textiles with an enhanced hydrophobicity and water column. Grafting of trans-cyclohexanediol isobutyl POSS (POSS-OH) to the biobased polymer backbone has also been investigated for the first time and its properties compared to a standard chain extender, 1,3-propanediol (PDO). The chemical structure of WPUD has been characterized by Fourier-transform infrared spectroscopy (FTIR) and nuclear magnetic resonance (NMR). The thermal properties have been evaluated by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). Mechanical properties have been studied by tensile stress–strain analysis. Moreover, the particle size, particle size distribution (PSD), and stability of developed waterborne dispersions have been assessed by dynamic light scattering (DLS), Z-potential, storage aging tests, and accelerated aging tests by analytical centrifuge (LUM). Subsequently, selected fabrics have been face-coated by the WPUD using the knife coating method and their properties have been assessed by measuring the water contact angle (WCA), oil contact angle (OCA), water column, fabric stiffness, air permeability, and water vapor resistance (breathability). Finally, the surface morphology and elemental composition of uncoated and coated fabrics have been studied by scanning electron microscopy (SEM) and energy-dispersive X-ray spectroscopy (EDS), respectively. All of the synthesized polyurethane-ureas provided the coated substrates with a remarkable hydrophobicity and water column, resulting in a more sustainable alternative to waterproof coatings based on fluoropolymers, such as PTFE. Grafting POSS-OH to the polymeric backbone has led to textile coatings with enhanced hydrophobicity, maintaining thermal, mechanical, and water column properties, giving rise to multifunctional coatings that are highly demanded in protective workwear and technical textiles.

Fluorinated chemicals, commonly known as per- and polyfluoroalkyt substances (PFASs), are widely used to obtain water-, oil- and stain-repellent texUles. The constant development and optimization of fluorochemicals for textile applications initiated more than five decades ago has resulted in a veryefficient DWOR-technology and texUles with exceptional hydro­ and oleo-phobic properties (DWOR acronym stands for Durable Water and Oil Repellen!). However, PFASs' high mobility, persistence and harmful health effects, has been proved by numerous scientific studies and, therefore, regulation and phase-out of severa! PFASs is being implemented bygovernm ents. At the present time the textile industry lacks suitable alternatives to fluorochemicals with comparable material characteristics. The main goal ofthis work is to design fluorine-free textile finishing agents based on sustainable polymers with low surface-tension functional groups in combination with (nano)materiaIs to confer water- and oil-repellencyto textiles as well as advanced multifunctionalities.Therefore, synergies of new available bio-based building-blocks, polymer synthesis and (nano)materiaIs have been explored to develop new finishing agents able to provide water and oil repellence to fabrics, without using fluorine-containing chemicals. In this work two different chemistries to confer water- and oil-repellence to textiles have been studied. In research line 1, biobased polyurethane-ureas have been developed. Obtained waterborne polyurethane-urea dispersions (WPUD) show good mechanical and thermal properties and therefore were chosen to be coated onto fabrics byknife-coating. In this way we were able to coat one side ofthe fabrics with a continuous polyurethane-urea film, capable of drastically reducing the permeability of the textiles to water and thus conferring remarkable hydrostatic pressure values to the treated fabrics. Therefore, ease offilming ofthe obtained WPUD make them good candidates to substitute PTFE inner membranes in technical fabrics. In research line 2, new fluorine-free waterborne (co)polymethacrytates have been developed. These polymethacrytates offer excellent performance when applied to fabric bythe padding method, i.e., by total immersion ofthe fabric in the finishing liquor, squeezing at controlled speed and pressure, and subsequent drying and curing. Unlike research line 1, here the coatings obtained do not significantly increase the stiffness ofthe fabrics nor significantly reduce their air permeability. This is dueto the fact that the polymethacrytate creates a thin coating on the surface of each individual libre, giving rise to "jacketed libres" instead a continuous film on one ofthe fabric's faces. Thanks to this, highlyhydrophobic breathable fabrics with reasonablygood oleophobic properties againstfattytriglycerides have been achieved. Therefore, these polymethacrytates are good candidates to substitute side-chain perfluorinated polymers in fabric's outer !ayer by more sustainable fluorine-free alternatives. lt is important to highlight that ali the developments reported in this work are stable waterborne formulations able to be applied by standard procedures and facilities in large-scale texUle production, thus reducing its entry barrier to textile finishing industry. Finally, it is worth emphasizing the complementarity of the two developed lines of research, providing the textile sector with an open window to valid, sustainable and fluorine-free solutions to achieve high-performance DWOR finishes Los productos químicos fluorados, comúnmente conocidos como sustancias per- y polifluoroalquiladas (PFASs), se utilizan ampliamente para obtener textiles que repelen el agua, el aceite y las manchas. El constante desarrollo y optimización de los fluoroquímicos para aplicaciones textiles iniciado hace más de cinco décadas ha dado como resultado una tecnología DWOR (Durable Water and Oil Repellent) muy eficiente y textiles con propiedades hidrofóbicas y oleofóbicas excepcionales. Sin embargo, la alta movilidad, la persistencia y los efectos nocivos para la salud de las PFASs han sido corroborados por numerosos estudios científicos y, por lo tanto, los gobiernos están implementando la regulación y eliminación de varias PFAS. En la actualidad, la industria textil carece de alternativas adecuadas a los fluoroquímicos con características y prestaciones comparables. El objetivo principal de la Tesis es diseñar agentes de acabado textil sin flúor, basados en polímeros sostenibles con grupos funcionales de baja tensión superficial en combinación con (nano)materiales, para conferir repelencia al agua y al aceite a los textiles, así como multifuncionalidades avanzadas. Por consiguiente, se han explorado las sinergias de nuevos monómeros bio-basados, la síntesis de polímeros y los (nano)materiales para desarrollar nuevos agentes de acabado capaces de proporcionar repelencia al agua y al aceite a los tejidos, sin utilizar productos químicos que contengan flúor. En este trabajo se han estudiado dos químicas diferentes para conferir repelencia al agua y al aceite a los textiles. En la línea de investigación 1 se han desarrollado poliuretano-ureas parcialmente bio-basados de elevada hidrofobicidad en forma de dispersiones acuosas exentas de compuestos fluorados. Dichas dispersiones presentan buenas propiedades mecánicas, térmicas y de formación de film, permitiendo la obtención de textiles técnicos mediante recubrimiento por rasqueta con buenas prestaciones de presión hidrostática. En algunos casos se han utilizado nanopartículas para maximizar prestaciones y conferir multifuncionalidades avanzadas. En la línea de investigación 2 se han desarrollado nuevos polimetacrilatos base agua libres de flúor. Estos...