Elaboration of polymers for 100% biobased composite materials with reduced environnemental impact

L’entreprise DIAM Bouchage développe des matériaux composites à base de farine de liège et de liant pour l’élaboration de bouchons technologiques mis en forme par moulage. DIAM souhaite remplacer le liant actuel à base de polyuréthanes par un nouveau polymère 100% biosourcé permettant de s’affranchir de l’utilisation d’isocyanates et de composés classifiés CMR. Pour cela, les Non-Isocyanate PolyUréthanes (NIPUs), et plus particulièrement les Polyhydroxyuréthanes (PHUs), ont été choisis. Ces travaux de thèse présentent donc la synthèse, la caractérisation et la formulation d’un nouveau liant PHU à base de cyclocarbonates et d’amines.Parmi les réactifs biosourcés et les différentes voies de synthèse des cyclocarbonates, plusieurs composés ont été sélectionnés en cohérence avec le cahier des charges. Cette sélection a ensuite mené à l’élaboration de matériaux PHUs et de bouchons composites afin d’identifier les formulations les plus prometteuses pour l’application visée. De nouvelles voies hybrides ont finalement été envisagées pour résoudre les problèmes liés aux faibles conversion et réactivité des PHUs. L’utilisation d’acrylates en tant qu’additifs réactifs ou réticulants de prépolymères PHU-amino téléchéliques a tout d’abord été décrite. Afin de répondre aux problématiques de mise en œuvre, de nouveaux monomères cyclocarbonate-siloxanes ont également été synthétisés afin d’obtenir des monomères fonctionnels de faible viscosité.DIAM Bouchage develops composites from cork flour and binder in order to produce technological cork-stoppers carried out by a molding process. To get rid of the use of isocyanates for polyurethanes synthesis, new pathways for 100% biobased polymers without the use of CMR substances are considered. As the most promising route for Non-Isocyanate PolyUrethanes (NIPUs) synthesis, Polyhydroxyurethanes (PHUs) have been chosen. The presented study concerns the synthesis, the characterization and the formulation of a new PHU binder from cyclocarbonates and amines.Among available biobased reactants and synthetic pathways, few monomers have been selected in accordance with specifications. This has led to PHUs materials and cork-stoppers development to identify the best formulations. New hybrids routes have finally been developed to overcome PHUs limitations such as reactivity and conversion. Acrylates have been used as reactive additives or cross-linkers for PHU-amino telechelic prepolymers. New cyclic carbonates monomers of low viscosity and high functionality have also been synthesized to solve process issues

Hybrid polyhydroxyurethanes: How to overcome limitations and reach cutting edge properties?

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Synthesis of sol-gel hybrid polyhydroxyurethanes

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Linseed Oil‐Based Thermosets by Aza‐Michael Polymerization

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From the synthesis of biobased cyclic carbonate to polyhydroxyurethanes: a promising route towards renewable NonIsocyanate Polyurethanes

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Synthesis of hybrid polyhydroxyurethanes by Michael addition

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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

From multi-functional siloxane-based cyclic carbonates to hybrid polyhydroxyurethane thermosets

International audienceIn this study, various novel cyclic carbonate-siloxane monomers were synthesized by hydrosilylation and CO2 carbonation of allyl glycidyl ether and epoxy-eugenol functions. Different structures were obtained from cyclic siloxane (D4) or linear PMHS-PDMS polymers with dangling cyclic carbonate functions. This hybrid route gives access to highly functional and low viscous cyclic carbonate monomers. Cyclic siloxane-carbonate monomers were reacted with 1,5-diamino-2-methylpentane (DYTEK-A) and 1,3-cyclohexanebis(methylamine) (CBMA) to afford polyhydroxyurethane (PHUs) thermosets as non-isocyanate polyurethanes (NIPUs) with high conversions and good reactivity. PHU thermosets were characterized to compare the thermal and mechanical properties of those different structures. The impact of the functionality was highlighted with different functional oligomers playing on cross-linking density of materials. D4 structure led to short and functional star shape monomers and afforded polymers with the highest mechanical properties. Eugenol, with an aromatic moiety, increased the stiffness and the thermal stability of PHU thermosets. Such hybrid PHU-siloxanes polymers combined flexibility of siloxanes with high mechanical performances of urethane groups

Fatty acid-based cross-linkable polymethacrylate coatings

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