Advances in waterborne polyurethane and polyurethane-urea dispersions and their eco-friendly derivatives: a review

Polyurethanes and polyurethane-ureas, particularly their water-based dispersions, have gained relevance as an extremely versatile area based on environmentally friendly approaches. The evolution of their synthesis methods, and the nature of the reactants (or compounds involved in the process) towards increasingly sustainable pathways, has positioned these dispersions as a relevant and essential product for diverse application frameworks. Therefore, in this work, it is intended to show the progress in the field of polyurethane and polyurethane-urea dispersions over decades, since their initial synthesis approaches. Thus, the review covers from the basic concepts of polyure-thane chemistry to the evolution of the dispersion’s preparation strategies. Moreover, an analysis of the recent trends of using renewable reactants and enhanced green strategies, including the current legislation, directed to limit the toxicity and potentiate the sustainability of dispersions, is described. The review also highlights the strengths of the dispersions added with diverse renewable additives, namely, cellulose, starch or chitosan, providing some noteworthy results. Similarly, dispersion’s potential to be processed by diverse methods is shown, evidencing, with different examples, their suitability in a variety of scenarios, outstanding their versatility even for high requirement applications.This research was funded by the University of the Basque Country (UPV/EHU) (GIU18/216 Research Group), the Spanish Ministry of Science, Innovation and Universities and European Union (MICINN/EU/FEDER) (MAT2016-76294-R and PID2019-105090RB-I00). Also, the Foundation for Science and Technology (FCT, Portugal) funded by financial support by national funds FCT/MCTES to CIMO (UIDB/00690/2020). National funding by FCT- Foundation for Science and Technology, through the institutional scientific employment program-contract with I.F.info:eu-repo/semantics/publishedVersio

Copolímeros de poliuretano do tipo poli[(hexametileno-carbamato- butanodiol)-co-(carbonato-co-éster)]

Los poliuretanos segmentados termoplástico elastoméricos (PUSTE) comprenden una familia de materiales muy versátiles debido a su su potencial empleo en diversos campos tales como biomedicina. Entre los PUSTE los formados por policarbonatos dioles y diisocianatos alifáticos son especialmente atractivos debido a su bioestabilidad y biocompatibilidad. En este trabajo se presentan los resultados del análisis morfológico y conducta mecánica de una familia de PUSTEs formados por 1,6-hexametilen diisocianato (HDI), 1,4-butanodiol (BD) y un copolímero cauchoso de policaprolactona y polihexametilen carbonato diol, PCL-b-PHMC-b-PCL, sintetizados con distinta relación entre bloques rígidos (HDI-BD) y copolímero cauchoso.Segmented thermoplastic polyurethane elastomers (PUSTE) comprise a family of very versatile materials with large potential for their applicability in different fields such as biomedicine. Among the PUSTEs the ones formed by polycarbonates diols and aliphatic diisocyanates are especially attractive due to their bioestability and biocompativility. In this work we present the results of morphological and mechanical characterization of different PUSTEs formed by 1,6-hexamethyene diisocyanate, 1,4-butanediol and a copolymer of polycaprolactone and polyhexamethylene carbonate diol, PCL-b-PHMC-b-PCL, synthesized with different ratios between rigid (HDI-BD) segments and the rubbery copolymer.Os poliuretanos segmentados termoplástico elastoméricos (PUSTE) compõem uma família de materiais versátil devido ao seu potencial uso em diversas áreas tais como biomedicina. Entre o PUSTE aqueles formaram por policarbonato dióis e diisocianatos alifáticos são especialmente atraentes porque seu biostability e biocompatibilidade. Este trabalho apresenta os resultados da análise morfológica e comportamento mecânico de uma família de PUSTEs é composto por 1,6-hexametilen diisocianato (HDI), 1,4-butanodiol (BD) e um copolímero de policaprolactona e polihexametilen carbonato de diol, PCL-b-PHMC-b-PCL, sintetizado com proporção diferente de copolímero de cauchoso de blocos rígida (HDI-BD)

Copolímeros de poliuretano do tipo poli[(hexametileno-carbamato- butanodiol)-co-(carbonato-co-éster)]

Los poliuretanos segmentados termoplástico elastoméricos (PUSTE) comprenden una familia de materiales muy versátiles debido a su su potencial empleo en diversos campos tales como biomedicina. Entre los PUSTE los formados por policarbonatos dioles y diisocianatos alifáticos son especialmente atractivos debido a su bioestabilidad y biocompatibilidad. En este trabajo se presentan los resultados del análisis morfológico y conducta mecánica de una familia de PUSTEs formados por 1,6-hexametilen diisocianato (HDI), 1,4-butanodiol (BD) y un copolímero cauchoso de policaprolactona y polihexametilen carbonato diol, PCL-b-PHMC-b-PCL, sintetizados con distinta relación entre bloques rígidos (HDI-BD) y copolímero cauchoso.Segmented thermoplastic polyurethane elastomers (PUSTE) comprise a family of very versatile materials with large potential for their applicability in different fields such as biomedicine. Among the PUSTEs the ones formed by polycarbonates diols and aliphatic diisocyanates are especially attractive due to their bioestability and biocompativility. In this work we present the results of morphological and mechanical characterization of different PUSTEs formed by 1,6-hexamethyene diisocyanate, 1,4-butanediol and a copolymer of polycaprolactone and polyhexamethylene carbonate diol, PCL-b-PHMC-b-PCL, synthesized with different ratios between rigid (HDI-BD) segments and the rubbery copolymer.Os poliuretanos segmentados termoplástico elastoméricos (PUSTE) compõem uma família de materiais versátil devido ao seu potencial uso em diversas áreas tais como biomedicina. Entre o PUSTE aqueles formaram por policarbonato dióis e diisocianatos alifáticos são especialmente atraentes porque seu biostability e biocompatibilidade. Este trabalho apresenta os resultados da análise morfológica e comportamento mecânico de uma família de PUSTEs é composto por 1,6-hexametilen diisocianato (HDI), 1,4-butanodiol (BD) e um copolímero de policaprolactona e polihexametilen carbonato de diol, PCL-b-PHMC-b-PCL, sintetizado com proporção diferente de copolímero de cauchoso de blocos rígida (HDI-BD)

Green nanocomposites from Salvia-based waterborne polyurethane-urea dispersions reinforced with nanocellulose

Waterborne polyurethane-urea (WBPUU) dispersions, products having none or low contents of organic solvents, depending on the used synthesis process, can provide suitable environmentally-friendly strategies to prepare novel materials. Moreover, waterborne systems enable the incorporation of aqueous dispersible nanoentities and soluble additives, which provides a strategy to design versatile functional materials with tailored properties. Having demonstrated in previous work the bacteriostatic properties of a 3 wt% Salvia-based WBPUU against Staphylococcus aureus, Escherichia coli and Pseudomonas aeruginosa, this work is focused in the preparation of Salvia-based WBPUU added with cellulose nanocrystals (CNC) tackling the preparation of functional green nanocomposite films with increased mechanical properties. Through this strategy, nanocomposites loaded with 1, 3 and 5 wt% of CNC were prepared, showing an effective CNC incorporation avoiding agglomerates. CNC addition is able to modulate soft and hard phase's segregation, inducing enhanced mechanical stiffness, together with improved deformability, while retarding thermomechanical instability to higher temperatures.Financial support from the University of the Basque Country (UPV/ EHU) (GIU18/216 Research Group), the Spanish Ministry of Economy and Competitiveness (MINECO) (MAT2016-76294-R). Foundation for Science and Technology (FCT, Portugal) for financial support by national funds FCT/MCTES to CIMO (UIDB/00690/2020). National funding by FCT- Foundation for Science and Technology, through the institutional scientific employment program-contract with I.P. Fernandes. We also wish to acknowledge the “Macrobehaviour-Mesostructure- Nanotechnology” SGIker units from the UPV/EHU, for their technical supporinfo:eu-repo/semantics/publishedVersio

Bacterial-cellulose-derived carbonaceous electrode materials for water desalination via capacitive method: The crucial role of defect sites

Electrosorptive desalination is a very simple and appealing approach to satisfy the increasing demand for drinking water. The large-scale application of this technology calls for the development of easy-to-produce, cheap and highly performing electrode materials and for the identification and tailoring of their most influential properties, as well. Here, biosynthesised bacterial cellulose is used as a carbon precursor for the production of three-dimensional nanostructures endowed with hierarchically porous architecture and different density and type of intrinsic and hetero-atom induced lattice defects. The produced materials exhibit unprecedented desalination capacities for carbon-based electrodes. At an initial concentration of 585 mg L−1 (10 mmol L−1), they are able to remove from 55 to 79 mg g−1 of salt; as the initial concentration rises to 11.7 g L−1 (200 mmol L−1), their salt adsorption capacity reaches values ranging between 1.03 and 1.35 g g−1. The results of the thorough material characterisation by complementary techniques evidence that the relative amount of oxygenated surface functional species enhancing the electrode wettability play a crucial role at lower NaCl concentrations, whereas the availability of active non-sp2 defect sites for adsorption is mainly influential at higher salt concentrations.L.U., M.A.C. and A.E. gratefully thank GIU18/216 - UPV/EHU Research Group for the financial support to their work

Copolímeros de poliuretano del tipo poli[(hexametilencarbamatobutanodiol)- co-(carbonato-co-éster)]

Los poliuretanos segmentados termoplástico elastoméricos (PUSTE) comprenden una familia de materiales muy versátiles debido a su potencial empleo en diversos campos tales como biomedicina. Entre los PUSTE los formados por policarbonatos dioles y diisocianatos alifáticos son especialmente atractivos debido a su bioestabilidad y biocompatibilidad. En este trabajo se presentan los resultados del análisis morfológico y conducta mecánica de una familia de PUSTEs formados por 1,6-hexametilen diisocianato (HDI), 1,4-butanodiol (BD) y un copolímero cauchoso de policaprolactona y polihexametilen carbonato diol, PCL-b-PHMC-b-PCL, sintetizados con distinta relación entre bloques rígidos (HDI-BD) y copolímero cauchoso

Advances in Waterborne Polyurethane and Polyurethane-Urea Dispersions and Their Eco-friendly Derivatives: A Review

Polyurethanes and polyurethane-ureas, particularly their water-based dispersions, have gained relevance as an extremely versatile area based on environmentally friendly approaches. The evolution of their synthesis methods, and the nature of the reactants (or compounds involved in the process) towards increasingly sustainable pathways, has positioned these dispersions as a relevant and essential product for diverse application frameworks. Therefore, in this work, it is intended to show the progress in the field of polyurethane and polyurethane-urea dispersions over decades, since their initial synthesis approaches. Thus, the review covers from the basic concepts of polyurethane chemistry to the evolution of the dispersion’s preparation strategies. Moreover, an analysis of the recent trends of using renewable reactants and enhanced green strategies, including the current legislation, directed to limit the toxicity and potentiate the sustainability of dispersions, is described. The review also highlights the strengths of the dispersions added with diverse renewable additives, namely, cellulose, starch or chitosan, providing some noteworthy results. Similarly, dispersion’s potential to be processed by diverse methods is shown, evidencing, with different examples, their suitability in a variety of scenarios, outstanding their versatility even for high requirement applications

Comparative effects of two different crosslinkers on the properties of vegetable oil-based polyurethanes

Thermoset polyurethanes (PUs) were prepared from a polyol derived from castor oil, 4,4′-methylene diphenyl diisocyanate (MDI) and different trifunctional low-molecular-weight crosslinkers, biobased glycerol (Gly) and petroleum-derived trimethylolpropane (TMP). The synthesis was carried out in bulk and without catalyst via one-step polymerization varying the components equivalent weight ratio, Polyol:MDI:Gly and Polyol:MDI:TMP, respectively. The physicochemical, morphological, thermal, dynamic–mechanical, and mechanical properties of the PUs were determined. The success of the reaction between the polyol and MDI was confirmed by Fourier transform infrared spectroscopy. The dynamic–mechanical and the mechanical properties as well as hardness were determined and related to the concentration of the low-molecular-weight crosslinkers utilized (Gly or TMP). However, important differences were observed between the synthesized two series, due to phase separation produced during the curing reaction, which affected more the materials prepared from TMP. Scanning electron microscopy images and dynamic–mechanical results confirmed this difference, related to the reactivity of primary and secondary hydroxyls present in the crosslinkers. Thermogravimetric analysis also showed to be sensible to the different structure of the crosslinkers with TMP leading to more thermally stable samples. Finally, measurements of water contact angle indicated that the surfaces were mostly hydrophobic with minor differences between the samples.Fil: Meiorin, Cintia. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mar del Plata. Instituto de Investigaciones en Ciencia y Tecnología de Materiales. Universidad Nacional de Mar del Plata. Facultad de Ingeniería. Instituto de Investigaciones en Ciencia y Tecnología de Materiales; ArgentinaFil: Calvo-Correas, Tamara. Universidad del País Vasco; EspañaFil: Mosiewicki, Mirna Alejandra. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mar del Plata. Instituto de Investigaciones en Ciencia y Tecnología de Materiales. Universidad Nacional de Mar del Plata. Facultad de Ingeniería. Instituto de Investigaciones en Ciencia y Tecnología de Materiales; ArgentinaFil: Aranguren, Mirta Ines. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mar del Plata. Instituto de Investigaciones en Ciencia y Tecnología de Materiales. Universidad Nacional de Mar del Plata. Facultad de Ingeniería. Instituto de Investigaciones en Ciencia y Tecnología de Materiales; ArgentinaFil: Corcuera, Maria Angeles. Universidad del País Vasco; EspañaFil: Eceiza, Arantxa. Universidad del País Vasco; Españ

Lignocellulosic Biomass as a Source of Raw Materials for the Synthesis of Polyurethanes

Precursors have been satisfactorily synthesized from lignocellulosic biomass for later use in the synthesis of polyurethanes resulting in competitive final properties with those of petroleum derived polyurethanes