Preparation and Characterization of Novel Poly(thiourethane)-Poly(isocyanurate) Covalent Adaptable Networks: Effect of the Catalysts.

Poly(thiourethane)-based covalent adaptable networks are synthesized by reacting a trimer of hexamethylene diisocyanate (Desmodur N3300) containing isocyanurate groups in its structure with 1,6-hexanedithiol. The catalysts evaluated for this process include dibutyltin dilaurate (DBTDL), lanthanum triflate (La(OTf)), and a thermal precursor of 1,8-diazabicyclo[5.4.

Strategies towards Fully Recyclable Commercial Epoxy Resins: Diels-Alder Structures in Sustainable Composites.

The Diels-Alder equilibrium is a widely known process in chemistry that can be used to provide a thermoset structure with recyclability and reprocessability mechanisms. In this study, a commercial epoxy resin is modified through the integration of functional groups into the network structure to provide superior performance. The present study has demonstrated that it is possible to adapt the curing process to efficiently incorporate these moieties in the final structure of commercial epoxy-based resins.

A Biobased Epoxy Vitrimer with Dual Relaxation Mechanism: A Promising Material for Renewable, Reusable, and Recyclable Adhesives and Composites.

This study presents the synthesis of a novel biobased epoxy monomer derived from vanillin and cystamine, incorporating imine and disulfide exchangeable groups within its structure. A series of epoxy-based vitrimers with two simultaneous exchange relaxation processes have been produced using this monomer. These exchange mechanisms operate without the need for any catalyst.

Biobased Imine Vitrimers Obtained by Photo and Thermal Curing Procedures-Promising Materials for 3D Printing.

Imine-based vitrimers were prepared from synthesized diimine-dimethacrylate monomer derived from biobased vanillin. First, a methacrylate derivative starting from vanillin was synthesized. The diimine derivative was synthesized by condensation of the aldehyde groups from two vanillin methacrylate units with the amine groups of hexamethylenediamine (HMDA).

Structural and mechanical analysis on mannuronate-rich alginate gels and xerogels beads based on Calcium, Copper and Zinc as crosslinkers.

Beads based on a mannuronate(M)-rich alginate (86 % M units) were prepared by adding the polysaccharide solution to a crosslinking bath containing different concentrations (0.5, 2 and 10 wt%) of XCl where X = Ca, Cu or Zn. Primarily focus was on Zn, due to its antioxidant, anti-inflammatory and anti-microbial capabilities.

Preparation and Characterization of a Series of Self-Healable Bio-Based Poly(thiourethane) Vitrimer-like Materials.

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.

Design and assembly of biodegradable capsules based on alginate hydrogel composite for the encapsulation of blue dye.

The encapsulation of bluing agents in biodegradable polymeric capsules is an emerging option in laundry detergents sector to substitute formaldehyde-based polymers, because they are non-biodegradable, carcinogenic and toxic. In this work, we present for the first time the successful encapsulation of a blue dye in biodegradable capsules which shell was formed by an alginate hydrogel and a polyethylene glycol network. Different types of capsules were synthesized (addition or not of the diacrylate monomer) and irradiation of the crosslinking solution at different times.

Dielectric Properties in Oriented and Unoriented Membranes Based on Poly(Epichlorohydrin-co-Ethylene Oxide) Copolymers: Part III.

The dielectric spectra and conductivity properties of neat poly(epichlorohydrin-co-ethylene oxide)(PECH-co-EO) copolymer and two modified copolymers with a 20% or 40% of dendron 3,4,5-tris[4-(-dodecan-1-yloxy)benzyloxy] benzoate units were analysed. A process of thermal orientation was applied to the copolymers to fine-tune the molecular motion of the side chains and determine their validity for cation transport materials. The study was conducted using Dielectric Thermal Analysis (DETA).

Membranes for Cation Transport Based on Dendronized Poly(epichlorohydrin-co-ethylene oxide). Part 1: The Effect of Dendron Amount and Column Orientation on Copolymer Mobility.

Dendronized polyethers give rise to columnar LC structures which can successfully act as cation transport materials. Therefore, we prepared two different materials, based on Poly(epichlorohydrin-co-ethylene oxide) (PECH-co-EO) grafted with methyl 3,4,5-tris[4-(n-dodecan-1-yloxy)benzyloxy] benzoate, containing 20% or 40% modified units, respectively. The obtained polymers were characterized by differential scanning calorimetry (DSC), X-ray diffraction and optical microscopy between crossed polars (POM) and compared to the unmodified PECH-co-EO.

From Supramolecular Hydrogels to Multifunctional Carriers for Biologically Active Substances.

Supramolecular hydrogels are 3D, elastic, water-swelled materials that are held together by reversible, non-covalent interactions, such as hydrogen bonds, hydrophobic, ionic, host-guest interactions, and metal-ligand coordination. These interactions determine the hydrogels' unique properties: mechanical strength; stretchability; injectability; ability to self-heal; shear-thinning; and sensitivity to stimuli, e.g.

Actuator Behaviour of Tailored Poly(thiourethane) Shape Memory Thermosets.

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.

Enhancement of 3D-Printable Materials by Dual-Curing Procedures.

Dual-curing thermosetting systems are recently being developed as an alternative to conventional curing systems due to their processing flexibility and the possibility of enhancing the properties of cured parts in single- or multi-stage processing scenarios. Most dual-curing systems currently employed in three-dimensional (3D) printing technologies are aimed at improving the quality and properties of the printed parts. However, further benefit can be obtained from control in the curing sequence, making it possible to obtain partially reacted 3D-printed parts with tailored structure and properties, and to complete the reaction by activation of a second polymerization reaction in a subsequent processing stage.

Recyclable Organocatalyzed Poly(Thiourethane) Covalent Adaptable Networks.

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.

The Use of Click-Type Reactions in the Preparation of Thermosets.

Click chemistry has emerged as an effective polymerization method to obtain thermosets with enhanced properties for advanced applications. In this article, commonly used click reactions have been reviewed, highlighting their advantages in obtaining homogeneous polymer networks. The basic concepts necessary to understand network formation via click reactions, together with their main characteristics, are explained comprehensively.

Bio-Based Epoxy Shape-Memory Thermosets from Triglycidyl Phloroglucinol.

A series of bio-based epoxy shape-memory thermosetting polymers were synthesized starting from a triglycidyl phloroglucinol (3EPOPh) and trimethylolpropane triglycidyl ether (TPTE) as epoxy monomers and a polyetheramine (JEF) as crosslinking agent. The evolution of the curing process was studied by differential scanning calorimetry (DSC) and the materials obtained were characterized by means of DSC, thermogravimetric analysis (TGA), dynamic mechanical analysis (DMA), stress-strain tests, and microindentation. Shape-memory properties were evaluated under free and totally constrained conditions.

Performance of Flexible Chemoresistive Gas Sensors after Having Undergone Automated Bending Tests.

Many sensors are developed over flexible substrates to be used as wearables, which does not guarantee that they will actually withstand being bent. This work evaluates the gas sensing performance of metal oxide devices of three different types, before and after having undergone automated, repetitive bending tests. These tests were aimed at demonstrating that the fabricated sensors were actually flexible, which cannot be taken for granted beforehand.

Rheological and Mechanical Characterization of Dual-Curing Thiol-Acrylate-Epoxy Thermosets for Advanced Applications.

Mechanical and rheological properties of novel dual-curing system based on sequential thiol-acrylate and thiol-epoxy reactions are studied with the aim of addressing the obtained materials to suitable advanced applications. The crosslinking process is studied by rheological analysis in order to determine conversion at gelation and the critical ratio. These parameters are used to discuss the intermediate material structure for each acrylate proportion and their possible application in the context of dual-curing and multi-step processing scenarios.

Effect of Selected Thiols on Cross-Linking of Acrylated Epoxidized Soybean Oil and Properties of Resulting Polymers.

The effect of the chemical structure and functionality of three structurally different thiols on the cross-linking of acrylated epoxidized soybean oil and on the properties of the resulting polymers was investigated in this study. 1,3-Benzenedithiol, pentaerythritol tetra(3-mercaptopropionate), and an hexathiol synthesized from squalene were used in the cross-linking of acrylated epoxidized soybean oil by thiol⁻Michael addition reaction. The reactivity of thiols determined from calorimetric curves followed the order: 1,3-benzenedithiol > pentaerythritol tetra(3-mercaptopropionate) > hexathiolated squalene.

Thermal and Mechanical Characterization of EMA-TEGDMA Mixtures for Cosmetic Applications.

Mixtures of methacrylic polymers are the most common materials for making composites to be used as resins for dental and cosmetic applications. Some of these mixtures are composed by poly(ethyl methacrylate) (PEMA) and poly(methyl methacrylate) (PMMA), which constitute a solid component to be mixed with a liquid component made out of methacrylate monomers. The reaction between the thermal initiator benzoyl peroxyde (BPO) present in the solid component and the activator of the polymerization process, ,-dimethyl--toluidine (DMT) present in the liquid component, gives rise to thermoset materials.

Epoxy-Based Shape-Memory Actuators Obtained via Dual-Curing of Off-Stoichiometric "Thiol⁻Epoxy" Mixtures.

In this work, epoxy-based shape-memory actuators have been developed by taking advantage of the sequential dual-curing of off-stoichiometric "thiol⁻epoxy" systems. Bent-shaped designs for flexural actuation were obtained thanks to the easy processing of these materials in the intermediate stage (after the first curing process), and successfully fixed through the second curing process. The samples were programmed into a flat temporary-shape and the recovery-process was analyzed in unconstrained, partially-constrained and fully-constrained conditions using a dynamic mechanical analyzer (DMA).