Synthesis of α,β-unsaturated esters of perfluoropolyalkylethers (PFPAEs) based on hexafluoropropylene oxide units for photopolymerization

α,β-unsaturated esters are usually synthesized for polymer applications. However, the addition of maleate (cis-configuration) to a fluorinated moiety is challenging due to its potential isomerization during esterification. Various synthetic routes were attempted and led to very low conversion or side-products. The immiscibility of both reagents combined with an easy isomerization or attack on the double bond were potential explanations. In this paper, the synthesis of maleates oligo(hexafluoropropylene oxide) is reported by Steglich esterification and the reaction conditions are discussed depending on the molecular weight of the fluorinated moieties. After UV-curing, hydrophobic polymers were obtained by copolymerization with vinyl ethers by electron acceptor–donor systems

Synthesis of sol-gel hybrid polyhydroxyurethanes

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Directed Studies Towards The Total Synthesis of (+)-13-Deoxytedanolide: Simple and Convenient Synthesis of C8-C16 Fragment

International audienceA straightforward synthesis of the enantioenriched C8-C16 south part of (+)-13-deoxytedanolide has been reported. The strength of this approach relies on the preparation of similar functionalized fragments via the transformation of a unique dihydrofuran building block through a 1,2-metallate rearrangement

Biobased phenol and furan derivatives coupling for the synthesis of functional monomers

International audienceGraphical Abstract Abstract Chemistry in general, but polymer chemistry in particular has to face the major challenge of finding solutions to ensure a sustainable and environmental-benign development of industry to answer consumer needs. Aromatics are very important chemical groups for polymer science for the synthesis of lots of thermostable or thermosetting polymers. However, most petrobased aromatic monomers (such as phenol) are toxic. Finding less toxic and sustainable aromatics is not easy because natural phenols have various functionalities in nature. In consequence aromatic-containing building blocks must be synthesized. The present review gives an overview of the different synthetic methods to prepare such aromatic building blocks by various coupling methods. It then focusses on the synthesis of CC bonds, on reductive coupling of natural aldehydes, on the carbonyl-aromatic coupling and on other various routes to prepare monomers. Indeed, owing to the rich reactivity and properties of aromatics, such functional monomers will undoubtedly lead to the development of high-added value polymers. This review also gives a brief overview of such potential applications

Cardanol‐Based Epoxy Monomers for High Thermal Properties Thermosets

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Cardanol and Eugenol Based Flame Retardant Epoxy Monomers for Thermostable Networks

Epoxy materials have attracted attention for many applications that require fireproof performance; however, the utilization of hazardous reagents brings about potential damage to human health. Eugenol and cardanol are renewable, harmless resources (according to ECHA) that allow the achievement of synthesis of novel phosphorylated epoxy monomers to be used as reactive flame retardants. These epoxy building blocks are characterized by 1H NMR and 31P NMR (nuclear magnetic resonance) and reacted with a benzylic diamine to give bio-based flame-retardant thermosets. Compared to DGEBA (Bisphenol A Diglycidyl Ether)-based material, these biobased thermosets differ by their cross-linking ratio, the nature of the phosphorylated function and the presence of an aliphatic chain. Eugenol has led to thermosets with higher glass transition temperatures due to a higher aromatic density. The flame-retardant properties were tested by thermogravimetric analyses (TGA), a pyrolysis combustion flow calorimeter (PCFC) and a cone calorimeter. These analyses demonstrated the efficiency of phosphorus by reducing significantly the peak heat release rate (pHRR), the total heat release (THR) and the effective heat of combustion (EHC). Moreover, the cone calorimeter test exhibited an intumescent phenomenon with the residues of phosphorylated eugenol thermosets. Lastly, the higher flame inhibition potential was highlighted for the phosphonate thermoset

Reactivity and kinetics of HDI-iminooxadiazinedione: Application to polyurethane synthesis

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Eugenol-based thermally stable thermosets by Alder-ene reaction: From synthesis to thermal degradation

International audiencePerforming thermostable materials such as phenolic or epoxy networks are classically obtained from petrobased and harmful monomers. In this study, alternative solutions based on renewable eugenol trifunctional monomer (TEP) are proposed. Thus, innovative biobased Alder-ene thermosets are prepared by reacting TEP with two different bismaleimides: N,N′-1,3-phenylene bismaleimide (PhBMI) and polydimethylsiloxane bismaleimide (SiBMI) leading to different crosslinked aromatic networks. These materials exhibit various mechanical properties with very different T g values of −113 °C and 247 °C for SiBMI and PhBMI materials respectively. However, both thermosets exhibit excellent thermal properties with elevated degradation temperature and high char yield. The degradation behavior was studied using thermogravimetric analysis – Fourier transformed infrared spectroscopy (TGA-FTIR): only silicon compounds were observed for SiBMI, whereas phosphorus and carbonaceous products had specific signatures in degradation gases for PhBMI. Kinetic analysis of degradation confirmed those different behaviors. Our contribution with two original Alder-ene thermosets is an innovative way to develop sustainable versatile high-performant materials

Improved “cure on demand” of aromatic bismaleimide with thiol triggered by retro-Diels-Alder reaction

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Fatty acid-based cross-linkable polymethacrylate coatings

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