Closed-loop recyclability of a biomass-derived epoxy-amine thermoset by methanolysis.

Epoxy resin thermosets (ERTs) are an important class of polymeric materials. However, owing to their highly cross-linked nature, they suffer from poor recyclability, which contributes to an unacceptable level of environmental pollution. There is a clear need for the design of inherently recyclable ERTs that are based on renewable resources. We present the synthesis and closed-loop recycling of a fully lignocellulose-derivable epoxy resin (DGF/MBCA), prepared from dimethyl ester of 2,5-furandicarboxylic acid (DMFD), 4,4'-methylenebis(cyclohexylamine) (MBCA), and glycidol, which displays excellent thermomechanical properties (a glass transition temperature of 170°C, and a storage modulus at 25°C of 1.2 gigapascals). Notably, the material undergoes methanolysis in the absence of any catalyst, regenerating 90% of the original DMFD. The diamine MBCA and glycidol can subsequently be reformed by acetolysis. Application and recycling of DGF/MBCA in glass and plant fiber composites are demonstrated.

Collagen/polyester-polyurethane porous scaffolds for use in meniscal repair.

Focusing on the regeneration of damaged knee meniscus, we propose a hybrid scaffold made of poly(ester-urethane) (PEU) and collagen that combines suitable mechanical properties with enhanced biological integration. To ensure biocompatibility and degradability, the degradable PEU was prepared from a poly(ε-caprolactone), L-lysine diisocyanate prepolymer (PCL di-NCO) and poly(lactic-co-glycolic acid) diol (PLGA). The resulting PEU (Mn = 52 000 g mol-1) was used to prepare porous scaffolds using the solvent casting (SC)/particle leaching (PL) method at an optimized salt/PEU weight ratio of 5 : 1. The morphology, pore size and porosity of the scaffolds were evaluated by SEM showing interconnected pores with a uniform size of around 170 µm. Mechanical properties were found to be close to those of the human meniscus (Ey ∼ 0.6 MPa at 37 °C). To enhance the biological properties, incorporation of collagen type 1 (Col) was then performed via soaking, injection or forced infiltration. The latter yielded the best results as shown by SEM-EDX and X-ray tomography analyses that confirmed the morphology and highlighted the efficient pore Col-coating with an average of 0.3 wt% Col in the scaffolds. Finally, in vitro L929 cell assays confirmed higher cell proliferation and an improved cellular affinity towards the proposed scaffolds compared to culture plates and a gold standard commercial meniscal implant.

Evaluation of Porous (Poly(lactide-co-glycolide)-co-(ε-caprolactone)) Polyurethane for Use in Orthopedic Scaffolds.

To develop an orthopedic scaffold that could overcome the limitations of implants used in clinics, we designed poly(ester-urethane) foams and compared their properties with those of a commercial gold standard. A degradable poly(ester-urethane) was synthetized by polyaddition between a diisocyanate poly(ε-caprolactone) prepolymer (PCL di-NCO, Mn = 2400 g·mol-1) and poly(lactic-co-glycolic acid) diol (PLGA, Mn = 2200 g·mol-1) acting as a chain extender. The resulting high-molecular-weight poly(ester-urethane) (PEU, Mn = 87,000 g·mol-1) was obtained and thoroughly characterized by NMR, FTIR and SEC-MALS. The porous scaffolds were then processed using the solvent casting (SC)/particle leaching (PL) method with different NaCl crystal concentrations. The morphology, pore size and porosity of the foams were evaluated using SEM, showing interconnected pores with a uniform size of around 150 µm. The mechanical properties of the scaffolds are close to those of the human meniscus (Ey = 0.5~1 MPa). Their degradation under accelerated conditions confirms that incorporating PLGA into the scaffolds greatly accelerates their degradation rate compared to the gold-standard implant. Finally, a cytotoxicity study confirmed the absence of the cytotoxicity of the PEU, with a 90% viability of the L929 cells. These results suggest that degradable porous PLGA/PCL poly(ester-urethane) has potential in the development of meniscal implants.

Paving the Way towards Sustainability of Polyurethanes: Synthesis and Properties of Terpene-Based Diisocyanate.

Due to growing concerns about environmental issues and the decline of petroleum-based resources, the synthesis of new biobased compounds for the polymer industry has become a prominent and timely topic. P-menthane-1,8-diamine (PMDA) is a readily available compound synthesized from turpentine, a cheap mixture of natural compounds isolated from pine trees. PMDA has been extensively used for its biological activities, but it can also serve as a source of valuable monomers for the polymer industry. In this work, commercial PMDA (ca. 85% pure) was purified by salinization, crystallization, and alkali treatment and then converted into p-menthane-1,8-diisocyanate (PMDI) through a phosgene-free synthesis at room temperature. A thorough analytical study using NMR techniques (1H, 13C, 13C-1H HSQC, 13C-1H HMBC, and 1H-1H NOESY) enables the characterization of the cis-trans isomeric mixtures of both PMDA and PMDI. These structural studies allowed for a better understanding of the spatial configuration of both isomers. Then, the reactivity of PMDI with a primary alcohol (benzyl alcohol) was studied in the presence of nine different catalysts exhibiting different activation modes. Finally, the use of PMDI in the synthesis of polyurethanes was explored to demonstrate that PMDI can be employed as a new biobased alternative to petrochemical-based isocyanates such as isophorone diisocyanate (IPDI).

One Step Closer to Coatings Applications Utilizing Self-Stratification: Effect of Rheology Modifiers.

Self-stratification of model blends of colloidal spheres has recently been demonstrated as a method to form multifunctional coatings in a single pass. However, practical coating formulations are complex fluids with upward of 15 components. Here, we investigate the influence of three different rheology modifiers (RMs) on the stratification of a 10 wt % 7:3 w:w blend of 270 and 96 nm anionic latex particles that do not stratify without RM. However, addition of a high molar mass polysaccharide thickener, xanthan gum, raises the viscosity and corresponding Péclet number enough to achieve small-on-top stratification as demonstrated by atomic force microscopy (AFM) measurements. Importantly, this was possible due to minimal particle-rheology modifier interactions, as demonstrated by the bulk rheology. In contrast, Carbopol 940, a microgel-based RM, was unable to achieve small-on-top stratification despite a comparable increase in viscosity. Instead, pH-dependent interactions with latex particles lead to either laterally segregated structures at pH 3 or a surface enrichment of large particles at pH 8. Strong RM-particle interactions are also observed when the triblock associative RM HEUR10kC12 is used. Here, small-on-top, large-enhanced, and randomly mixed structures were observed at respectively 0.01, 0.1, and 1 wt % HEUR10kC12. Combining rheology, dynamic light scattering, and AFM results allows the mechanisms behind the nonmonotonic stratification in the presence of associative RMs to be elucidated. Our results highlight that stratification can be predicted and controlled for RMs with weak particle interactions, while a strong RM-particle interaction may afford a wider range of stratified structures. This takes a step toward successfully harnessing stratification in coatings formulations.

Dynamic PEG-PLA/Hydroxyurethane Networks Based on Imine Bonds as Reprocessable Elastomeric Biomaterials.

The development of dynamic covalent chemistry opens the way to the design of materials able to be reprocessed by an internal exchange reaction under thermal stimulus. Imine exchange differs from other exchange reactions by its relatively low temperature of activation. In this study, amine-functionalized star-shaped PEG-PLA and an aldehyde-functionalized hydroxyurethane modifier were combined to produce PEG-PLA/hydroxyurethane networks incorporating imine bonds. The thermal and mechanical properties of these new materials were evaluated as a function of the initial ratio of amine/aldehyde used during synthesis. Rheological analyses highlighted the dynamic behavior of these vitrimers at moderate temperature (60-85 °C) and provided the flow activation energies. Additionally, the reprocessability of these PEG-PLA/hydroxyurethane vitrimers was assessed by comparing the material properties before reshaping and after three reprocessing cycles (1 ton, 1 h, 70 °C). Hence, these materials can easily be designed to satisfy a specific medical application without properties loss. This work opens the way to the development of a new generation of dynamic materials combining degradable PEG-PLA copolymers and hydroxyurethane modifiers, which could find applications in the shape of medical devices on-demand under mild conditions.

A Blooming Season for Natural Polymers and Biopolymers.

The year 2023 is particularly remarkable because we are celebrating the 25th anniversary of the 12 principles of Green Chemistry described in the groundbreaking book Green Chemistry: Theory and Practice co-authored by Paul Anastas and John C [...].

Dihydroxyacetone: A User Guide for a Challenging Bio-Based Synthon.

1,3-dihydroxyacetone (DHA) is an underrated bio-based synthon, with a broad range of reactivities. It is produced for the revalorization of glycerol, a major side-product of the growing biodiesel industry. The overwhelming majority of DHA produced worldwide is intended for application as a self-tanning agent in cosmetic formulations. This review provides an overview of the discovery, physical and chemical properties of DHA, and of its industrial production routes from glycerol. Microbial fermentation is the only industrial-scaled route but advances in electrooxidation and aerobic oxidation are also reported. This review focuses on the plurality of reactivities of DHA to help chemists interested in bio-based building blocks see the potential of DHA for this application. The handling of DHA is delicate as it can undergo dimerization as well as isomerization reactions in aqueous solutions at room temperature. DHA can also be involved in further side-reactions, yielding original side-products, as well as compounds of interest. If this peculiar reactivity was harnessed, DHA could help address current sustainability challenges encountered in the synthesis of speciality polymers, ranging from biocompatible polymers to innovative polymers with cutting-edge properties and improved biodegradability.

Influence of Phosphorus Structures and Their Oxidation States on Flame-Retardant Properties of Polyhydroxyurethanes.

This article focuses on the synthesis of polyhydroxyurethane (PHU) materials containing novel phosphorus flame retardants (FR). Four different phosphorus compounds were grafted onto cyclic carbonate: 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), diethyl phosphite (DEP), diphenyl phosphite (DPP) and dibenzo[d,f][1,3,2]dioxaphosphepine 6-oxide (BPPO). Thus, three novel phosphorus reactive cyclic carbonates which have never been reported so far were synthetized. Phosphorus FR containing PHU materials were characterized by FTIR to evidence the total conversion of the cyclic carbonate. Moreover, the gel contents up to 80% confirmed the formation of the polymer network. Then, the thermal stability and the flame-retardant properties were investigated by thermogravimetric analyses, cone calorimeter and pyrolysis combustion flow calorimeter. The mode of action of phosphorus compounds, depending on the oxidation state, was especially highlighted. Phosphonate (+III) provided better action in a condensed phase than phosphinate thanks to a more efficient char formation. Among phosphonates, differences were observed in terms of char-formation rate and expansion. DEP provided the best flame-retardant properties, with a reduction of 76% of pHRR with 2 wt% of phosphorus in cone calorimeter analysis. Therefore, this article highlighted the different modes of action of phosphorus flame retardants, depending on the oxidation state of phosphorus, in PHU materials.

Catalyst-Free Thia-Michael Addition to α-Trifluoromethylacrylates for 3D Network Synthesis.

Thia-Michael additions (1,4-additions of a thiol to a Michael acceptor) are generally catalyzed by an external Brønsted or Lewis base. A spontaneous (uncatalyzed) Michael addition of thiols to α-trifluoromethyl acrylates is described, as well as its application to the very efficient preparation of a thermoset. A thorough mechanistic investigation, based on an experimental kinetic study and on DFT calculations, is presented for the addition of arene- and alkanethiols to tert-butyl trifluoromethyl acrylate in polar aprotic solvents, unveiling a probable solvent-assisted proton transfer in the rate-determining step and a considerable lowering of the energy barrier induced by the CF3 group.

Thia-Michael Reaction: The Route to Promising Covalent Adaptable Networks.

While the Michael addition has been employed for more than 130 years for the synthesis of a vast diversity of compounds, the reversibility of this reaction when heteronucleophiles are involved has been generally less considered. First applied to medicinal chemistry, the reversible character of the hetero-Michael reactions has recently been explored for the synthesis of Covalent Adaptable Networks (CANs), in particular the thia-Michael reaction and more recently the aza-Michael reaction. In these cross-linked networks, exchange reactions take place between two Michael adducts by successive dissociation and association steps. In order to understand and precisely control the exchange in these CANs, it is necessary to get an insight into the critical parameters influencing the Michael addition and the dissociation rates of Michael adducts by reconsidering previous studies on these matters. This review presents the progress in the understanding of the thia-Michael reaction over the years as well as the latest developments and plausible future directions to prepare CANs based on this reaction. The potential of aza-Michael reaction for CANs application is highlighted in a specific section with comparison with thia-Michael-based CANs.

Phosphorus Modified Cardanol: A Greener Route to Reduce VolaTile Organic Compounds and Impart Flame Retardant Properties to Alkyd Resin Coatings.

Novel phosphorylated cardanol molecules based on phosphonate (PO3CR) and phosphate (PO4CR) functions were synthetized. Those molecules have two main actions which are described in this article: the reduction in volatile organic compounds (VOC) and the development of flame retardant (FR) properties conferred on alkyd resins used as coatings for wood specimen. Phosphorylated cardanol compounds have been successfully grafted by covalent bonds to alkyd resins thanks to an auto-oxidative reaction. The impact of the introduction of PO3CR and PO4CR on the film properties such as drying time and flexibility has been studied and the thermal and flame retardant properties through differential scanning calorimeter, thermogravimetric analysis and pyrolysis-combustion flow calorimeter. These studies underscored an increase in the thermal stability and FR properties of the alkyd resins. In the cone calorimeter test, the lowest pHRR was obtained with 3 wt% P of phosphate-cardanol and exhibited a value of 170 KW.m-2, which represented a decrease of almost 46% compared to the POxCR-free alkyd resins. Moreover, a difference in the mode of action between phosphonate and phosphate compounds has been highlighted. The most effective coating which combined excellent FR properties and good coating properties has been obtained with 2 wt% P of phosphate-cardanol. Indeed, the film properties were closed to the POxCR-free alkyd resin and the pHRR decreased by 41% compared to the reference alkyd resin.

Coordination Adaptable Networks: Zirconium(IV) Carboxylates.

Vitrimers are 3D "covalent adaptable networks" (CANs) with flow properties thanks to thermally activated associative exchange reactions. This contribution introduces coordination adaptable networks, or CooANs, that are topologically related to metal-organic frameworks with octahedral Zr6 clusters as secondary building units in a carboxylic acid-functionalized acrylate-methacrylate copolymer matrix. A series of Zr-CooAN-x materials (x=percent of Zr6 loading relative to maximum capacity) was synthesized with x=5, 10, 15, 20, 25, 50 and 100. The mechanical and rheological investigations demonstrate vitrimer-like properties for x up to 50, the crosslink migration being ensured by carboxylate ligand exchange, with relaxation becoming slower as the Zr6 content is increased. The flow activation energy of Zr-CooAN-10 is 92.9±3.6 kJ mol-1 . Rapid (30 min) hot-press reshaping occurs at temperatures in the 50-100 °C range under a 3-ton pressure and does not significantly alter the material properties.

Understanding the Reshaping of Fluorinated Polyester Vitrimers by Kinetic and DFT Studies of the Transesterification Reaction.

Vitrimers are a third class of polymers gathering the mechanical properties and solvent resistance of 3D thermosets and the reprocessability of thermoplastics. This unique behaviour is due to the triggering of certain covalent exchange reactions that allow the network to rearrange upon application of a stimulus. The constitutive feature of vitrimers is the adoption of a glass-like viscosity during the rearrangement of the network, often due to an associative mechanism for the exchange reaction. Transesterification networks are one of the most studied type of vitrimers that usually require the incorporation of a catalyst, implying the associated drawbacks. Following up on a recent report on catalyst-free transesterification vitrimers in which the ester functions are particularly reactive thanks to the presence of fluorine atoms in α- or ß-position, parallel DFT calculations and an experimental kinetic study on model molecules are presented in order to quantitatively assess the effect of neighbouring fluorinated groups on the transesterification reaction rate.

CNSL, a Promising Building Blocks for Sustainable Molecular Design of Surfactants: A Critical Review.

Surfactants are crystallizing a certain focus for consumer interest, and their market is still expected to grow by 4 to 5% each year. Most of the time these surfactants are of petroleum origin and are not often biodegradable. Cashew Nut Shell Liquid (CNSL) is a promising non-edible renewable resource, directly extracted from the shell of the cashew nut. The interesting structure of CNSL and its components (cardanol, anacardic acid and cardol) lead to the synthesis of biobased surfactants. Indeed, non-ionic, anionic, cationic and zwitterionic surfactants based on CNSL have been reported in the literature. Even now, CNSL is absent or barely mentioned in specialized review or chapters talking about synthetic biobased surfactants. Thus, this review focuses on CNSL as a building block for the synthesis of surfactants. In the first part, it describes and criticizes the synthesis of molecules and in the second part, it compares the efficiency and the properties (CMC, surface tension, kraft temperature, biodegradability) of the obtained products with each other and with commercial ones.

Thiol-Ene Coupling of High Oleic Sunflower Oil towards Application in the Modification of Flexible Polyurethane Foams.

High oleic sunflower oil-based polyol was obtained by thiol-ene coupling and applied in the preparation of flexible polyurethane foams. The photochemically initiated thiol-ene click reaction was carried out under UV irradiation using 2-mercaptoethanol. Bio-based polyol with hydroxyl value of 201.4 mg KOH/g was used as 30 wt% substituent of petrochemical polyether polyol in the formulations of flexible foams. Both reference foams, as well as foams modified with bio-based polyol, were formulated to have various isocyanate indices (0.85, 0.95, 1.05). Flexible foams were compared in terms of their thermomechanical properties and analyzed using FT-IR and SEM microscopy. Modification with bio-based polyol resulted in foams with superior compression properties, higher support factor, and lower resilience than reference foams. TGA and FT-IR curves confirmed the presence of urethane/urea and ether linkages in the polyurethane matrix. Moreover, double glass transition temperature corresponding to soft and hard segments of polyurethane was observed by DSC proving the phase-separated morphology.

Cascade (Dithio)carbonate Ring Opening Reactions for Self-Blowing Polyhydroxythiourethane Foams.

Polyurethane (PU) foams are very common materials that have found many applications over the years. Their use is constantly improving due to their unique physical properties and easy blowing which does not require the addition of a blowing agent. Greener routes have been explored in the recent years to replace isocyanates. One of the most promising routes is leading to polyhydroxyurethanes (PHU). However, with PHUs, external blowing agent are usually required to obtain a foam. Thus, the work focuses on PHU foam synthesis using in situ reaction to produce NIPU foam. Hence, the aminolysis of thiocyclic carbonate triggers Pearson reaction between released thiols and cyclic carbonates which serves as a chemical blowing agent.

Biobased Composites by Photoinduced Polymerization of Cardanol Methacrylate with Microfibrillated Cellulose.

Biobased monomers and green processes are key to producing sustainable materials. Cardanol, an aromatic compound obtained from cashew nut shells, may be conveniently functionalized, e.g., with epoxy or (meth)acrylate groups, to replace petroleum-based monomers. Photoinduced polymerization is recognized as a sustainable process, less energy intensive than thermal curing; however, cardanol-based UV-cured polymers have relatively low thermomechanical properties, making them mostly suitable as reactive diluents or in non-structural applications such as coatings. It is therefore convenient to combine them with biobased reinforcements, such as microfibrillated cellulose (MFC), to obtain composites with good mechanical properties. In this work a cardanol-based methacrylate monomer was photopolymerized in the presence of MFC to yield self-standing, flexible, and relatively transparent films with high thermal stability. The polymerization process was completed within few minutes even in the presence of filler, and the cellulosic filler was not affected by the photopolymerization process.

Solvent-Free Design of Biobased Non-isocyanate Polyurethanes with Ferroelectric Properties.

Increasing energy autonomy and lowering dependence on lithium-based batteries are more and more appealing to meet our current and future needs of energy-demanding applications such as data acquisition, storage, and communication. In this respect, energy harvesting solutions from ambient sources represent a relevant solution by unravelling these challenges and giving access to an unlimited source of portable/renewable energy. Despite more than five decades of intensive study, most of these energy harvesting solutions are exclusively designed from ferroelectric ceramics such as Pb(Zr,Ti)O3 and/or ferroelectric polymers such as polyvinylidene fluoride and its related copolymers, but the large implementation of these piezoelectric materials into these technologies is environmentally problematic, related with elevated toxicity and poor recyclability. In this work, we reveal that fully biobased non-isocyanate polyurethane-based materials could afford a sustainable platform to produce piezoelectric materials of high interest. Interestingly, these non-isocyanate polyurethanes (NIPUs) with ferroelectric properties could be successfully synthesized using a solvent-free reactive extrusion process on the basis of an aminolysis reaction between resorcinol bis-carbonate and different diamine extension agents. Structure-property relationships were established, indicating that the ferroelectric behavior of these NIPUs depends on the nanophase separation inside these materials. These promising results indicate a significant potential for fulfilling the requirements of basic connected sensors equipped with low-power communication technologies.

Eugenol, a Promising Building Block for Biobased Polymers with Cutting-Edge Properties.

Biobased materials, derived from biomass building blocks, are essential in the pursuit of sustainable materials. Eugenol, a natural phenol obtained from clove oil, but also from lignin depolymerization, possesses a chemical structure that allows its easy modification to obtain a broad and versatile platform of biobased monomers. In this Perspective, an overview of the variety of reactions that have been executed on the allylic double bond, phenol hydroxyl group, aromatic ring, and methoxy group is given, focusing our attention on those to obtain monomers suitable for different polymerization reactions. Furthermore, possible applications and perspectives on the eugenol-derived materials are provided.