Search Results (8)

Traditional marine antifouling coatings function through releasing toxic antifouling agents, causing serious harm to marine ecosystems. To address this challenge, an eco-friendly fluoro-silicon-modified polythiourethane (FSi-PTU) coating has been prepared via a polymerization reaction with dihydroxy propyl silicone oil (HO-PDMS-OH), 1H,1H,2H,2H-perfluorohexanol (FTOH), hexamethylene diisocyanate (HDI), and pentaerythritol tetrakis (3-mercaptopropionate) (PETMP). The FSi-PTU polymer incorporates siloxane segments and fluorinated side chains, which are inhomogeneously distributed on the coating surface and construct a hydrophobic surface. The FSi-PTU coating exhibits good hydrophobicity, strong adhesion (≥2.14 MPa), and improved mechanical properties. The antifouling properties of the FSi-PTU coating have been researched. The results of laboratory tests demonstrate that the FSi-PTU coating exhibits excellent anti-protein adsorption and anti-algal attachment performance. The FSi-PTU-2 coating shows certain antifouling properties in the actual seawater test for three months. The results provide a certain reference value for developing eco-friendly marine antifouling coatings. Full article

The global plastic waste problem has created an urgent need for the development of more sustainable materials and recycling processes. Polyurethane (PU) plastics, which represent 5.5% of globally produced plastics, are particularly challenging to recycle owing to their crosslinked structure. Covalent adaptable networks (CANs) based on dynamic covalent bonds have emerged as a promising solution for recycling PU waste. CANs enable the production of thermoset polymers that can be recycled using methods that are traditionally reserved for thermoplastic polymers. Reprocessing using hot-pressing techniques, in particular, proved to be more suited for the class of polyurethanes, allowing for the efficient recycling of PU materials. This Review paper explores the potential of CANs for improving the sustainability of PU recycling processes by examining different types of PU-CANs, bond types, and fillers that can be used to optimise the recycling efficiency. The paper concludes that further research is needed to develop more cost-effective and industrial-friendly techniques for recycling PU-CANs, as they can significantly contribute to sustainable development by creating recyclable thermoset polymers. Full article

In this study, poly(thiourethane) (PTU) with different structures is synthesized by click chemistry from trimethylolpropane tris(3-mercaptopropionate) (S3) and different diisocyanates (hexamethylene diisocyanate, HDI, isophorone diisocyanate, IPDI and toluene diisocyanate, TDI). Quantitative analysis of the FTIR spectra reveals that the reaction rates between TDI and S3 are the most rapid, resulting from the combined influence of conjugation and spatial site hindrance. Moreover, the homogeneous cross-linked network of the synthesized PTUs facilitates better manageability of the shape memory effect. All three PTUs exhibit excellent shape memory properties (R_r and R_f are over 90%), and an increase in chain rigidity is observed to negatively impact the shape recovery rate and fix rate. Moreover, all three PTUs exhibit satisfactory reprocessability performance, and an increase in chain rigidity is accompanied by a greater decrease in shape memory and a smaller decrease in mechanical performance for recycled PTUs. Contact angle (<90°) and in vitro degradation results (13%/month for HDI-based PTU, 7.5%/month for IPDI-based PTU, and 8.5%/month for TDI-based PTU) indicate that PTUs can be used as long-term or medium-term biodegradable materials. The synthesized PTUs have a high potential for applications in smart response scenarios requiring specific glass transition temperatures, such as artificial muscles, soft robots, and sensors. Full article

A series of poly(thiourethanes) (PTUs) from biobased monomers have been synthesized. Limonene and squalene were transformed into polyfunctional thiols by thiol-ene reaction with thioacetic acid and further saponification. They were then reacted in different proportions with hexamethylene diisocyanate (HDI) in the presence of a catalyst to prepare bio-based poly(thiourethane) vitrimer-like materials. The different functionalities of squalene and limonene thiols (six and two, respectively) allow for changing the characteristics of the final material by only varying their relative proportions in the reactive mixture. The proportions of thiol and isocyanate groups were stoichiometric in all the formulations tested. An acidic and a basic catalyst were tested in the preparation of the networked polymers. As the acidic catalyst, we selected dibutyltin dilaurate (DBTDL), and as the basic catalyst, a tetraphenylborate salt of 1,8-diazabicyclo(5.4.0)undec-7-ene (BGDBU), which has the advantage of only releasing the base at high temperatures. The materials obtained were characterized by thermogravimetry and thermomechanical analysis. The vitrimeric-like behavior was evaluated, and we could see that higher proportions of the limonene derivative in the formulations led to faster stress relaxation of the material. The use of the base catalyst led to a much shorter relaxation time. The materials obtained demonstrated good self-healing efficiency. Full article

In this work, a new family of poly(thiourethane) shape memory thermosetting actuators was developed and characterized. These materials can be easily prepared from mixtures of two different aliphatic diisocyanates and a trithiol in the presence of a latent catalyst, allowing an easy manipulation of the formulation. Rheological studies of the curing process confirm the latent character of the formulations. The glass transition temperatures and the mechanical properties can be modified by varying the proportion of diisocyanates (hexamethylene diisocyanate, HDI, and isophorone diisocyanate, IPDI) with stoichiometric amounts of trimethylolpropane tris(3-mercaptopropionate). The shape-memory behavior was deeply investigated under three different conditions: unconstrained, partially constrained, and fully constrained. Tests were performed in single cantilever bending mode to simulate conditions closer to real complex mechanics of thermomechanical actuators under flexural performances. The complex recovery process in single cantilever bending mode was compared with that obtained using tensile mode. The results evidenced that the amount of recovery force in fully constrained conditions, or energy released during the recovery process in partially constrained, can be modulated by simply changing the proportion of both diisocyanates. A simple model based on Timoshenko beam theory was used for the prediction of the amount of work performed. The reported results are an important guideline to design shape-memory materials based on poly(thiourethane) networks, establishing criteria for the choice of the material depending on the expected application. Full article

The attachment of bacteria and other microbes to natural and artificial surfaces leads to the development of biofilms, which can further cause nosocomial infections. Thus, an important field of research is the development of new materials capable of preventing the initial adhesion of pathogenic microorganisms. In this work, novel polymer/particle composite materials, based on a polythiourethane (PTU) matrix and either spherical (s-ZnO) or tetrapodal (t-ZnO) shaped ZnO fillers, were developed and characterized with respect to their mechanical, chemical and surface properties. To then evaluate their potential as anti-fouling surfaces, the adhesion of two different pathogenic microorganism species, Staphylococcus aureus and Candida glabrata, was studied using atomic force microscopy (AFM). Our results show that the adhesion of both S. aureus and C. glabrata to PTU and PTU/ZnO is decreased compared to a model surface polydimethylsiloxane (PDMS). It was furthermore found that the amount of both s-ZnO and t-ZnO filler had a direct influence on the adhesion of S. aureus, as increasing amounts of ZnO particles resulted in reduced adhesion of the cells. For both microorganisms, material composites with 5 wt.% of t-ZnO particles showed the greatest potential for anti-fouling with significantly decreased adhesion of cells. Altogether, both pathogens exhibit a reduced capacity to adhere to the newly developed nanomaterials used in this study, thus showing their potential for bio-medical applications. Full article

A new type of tetraphenylborate salts derived from highly basic and nucleophilic amines, namely 1,5-diazabicyclo[4.3.0]non-5-ene (DBN), 1,8-diazabicyclo(5.4.0)undec-7-ene (DBU) and triazabicyclodecene (TBD), was applied to the preparation of networked poly(thiourethane)s (PTUs), which showed a vitrimer-like behavior, with higher stress-relaxation rates than PTUs prepared by using dibutyl thin dilaurate (DBTDL) as the catalyst. The use of these salts, which release the amines when heated, instead of the pure amines, allows the formulation to be easily manipulated to prepare any type of samples. The materials prepared from stoichiometric mixtures of hexamethylene diisocyanate (HDI), trithiol (S3) and with a 10% of molar excess of isocyanate or thiol were characterized by FTIR, thermomechanical analysis, thermogravimetry, stress-relaxation tests and tensile tests, thus obtaining a complete thermal and mechanical characterization of the materials. The recycled materials obtained by grinding the original PTUs and hot-pressing the small pieces in the optimized time and temperature conditions were fully characterized by mechanical, thermomechanical and FTIR studies. This allowed us to confirm their recyclability, without appreciable changes in the network structure and performance. From several observations, the dissociative interchange trans-thiocarbamoylation mechanism was evidenced as the main responsible of the topological rearrangements at high temperature, resulting in a vitrimeric-like behavior. Full article

Ecological considerations strongly necessitate the development of environmentally friendly antifouling paints. A promising alternative to biocide containing antifouling paints are fouling-release coatings, which are non-toxic and designed to prevent permanent attachment of marine organisms to the surface, due to their low surface energy. However, these coatings suffer from insufficient mechanical properties, which make them unsuitable for mechanically stressed surfaces e.g., on ship hulls. To overcome those obstacles, polydimethylsiloxane (PDMS)-polythiourethane (PTU) composites modified with tetrapodal shaped micro-nano ZnO particles (t-ZnO) were produced and characterized by evaluating the surface energy, mechanical properties, and fouling-release performance. Among all variations, PTU/1 wt.% PDMS composites with 1 wt.% t-ZnO particles possess superior properties for applications as fouling-release coatings for maritime purposes. Full article