32 research outputs found
DimĂšres dâacides rĂ©siniques et de dĂ©rivĂ©s de la lignine : nouveaux prĂ©curseurs pour la synthĂšse de polymĂšres bio-sourcĂ©s
The aim of this thesis is to investigate new biobased rigid synthons for the synthesis of polymers with high thermomechanical properties. A polycyclic biobased molecule, i.e resinic acids, and phenolic compounds potentially derived from lignin, such as vanillin were selected. Both classes of substrates were dimerized in order to get difunctional symmetric synthons. On the one hand, abietic acid dimers synthesized via a cationic mechanism presented an ill-defined structure. To avoid reactivity issues, dimers with reactive terminal double bonds were successfully synthesized by esterification of abietic acid dimers with undecenol and polymerized by ADMET methodology. On the other hand, we developed a âgreenâ process to dimerize phenolic compounds derived from lignin in large quantity and high yield via enzymatic catalysis using a laccase. The main advantage of this method is that the phenolic monomer is soluble in the reaction medium while the dimer precipitates. After chemical modifications of the dimers, we built a functional bio-platform of biphenyl derivatives. The latter were then used for the synthesis of polyesters, polyamides and epoxy resins which exhibited remarkable thermal and thermomechanical properties.Ces travaux de thĂšse traitent de lâutilisation dâune molĂ©cule polycyclique, lâacide abiĂ©tique, issu de la colophane, et de dĂ©rivĂ©s phĂ©noliques potentiellement dĂ©rivĂ©s de la lignine, pour la synthĂšse de polymĂšres rigides bio-sourcĂ©s. Dans les deux cas, des monomĂšres symĂ©triques et difonctionnels sont Ă©laborĂ©s par rĂ©action de dimĂ©risation des prĂ©curseurs bio-sourcĂ©s puis testĂ©s en polymĂ©risation. Dâune part, les dimĂšres de lâacide abiĂ©tique obtenus par un mĂ©canisme cationique possĂšdent des structures mal dĂ©finies qui compliquent leur polymĂ©risation. Ces dimĂšres ont alors Ă©tĂ© estĂ©rifiĂ©s avec de lâundĂ©cĂ©nol afin dâobtenir un composĂ© bis-insaturĂ© qui est ensuite polymĂ©risĂ© par ADMET. Dâautre part, un procĂ©dĂ© de dimĂ©risation de molĂ©cules phĂ©noliques, potentiellement issues de la lignine, a Ă©tĂ© dĂ©veloppĂ© par voie enzymatique utilisant une laccase. Lâavantage majeur de ce procĂ©dĂ© âvertâ rĂ©side dans la sĂ©paration trĂšs simple entre le monomĂšre, soluble, et son dimĂšre, insoluble. Ces dimĂšres ont ensuite Ă©tĂ© modifiĂ©s chimiquement afin de constituer une bio-plateforme de composĂ©s biphĂ©nyles fonctionnels. Ces composĂ©s ont Ă©tĂ© utilisĂ©s pour la synthĂšse de polyesters, polyamides et rĂ©sines Ă©poxy qui prĂ©sentent des propriĂ©tĂ©s thermiques et thermomĂ©caniques remarquables
Synthesis and Characterization of Novel IsosorbideâBased Polyester Derivatives Decorated with α âAcyloxy Amides
The synergy of multicomponent reactions (MCRs) and metathesis chemistry is applied for the synthesis of bio-based functional isosorbide polymers (i.e., polyesters) decorated with α-acyloxy amide motif. The chemical structure of the polyesters that are not accessible by any other conventional methodologies is characterized in-depth via nuclear magnetic resonance, size-exclusion chromatography, and attenuated total reflectance infrared spectroscopy. It is also observed that the âbiomass-derivedâ carbon % of the polymers varied between 66.2 and 76.9. Moreover, the thermal properties of the novel isosorbide-based polymers are investigated via thermogravimetric analysis and differential scanning calorimetry, revealing that the polymers are in the amorphous state, identified by the glass transition temperature (T) values below the human body temperature. The mechanical properties and the biocompatibility of the functional novel polyester derivative with the highest âbiomass-derivedâ carbon % are evaluated via dynamic mechanical analysis and cytotoxicity test. The exemplary polymer is biocompatible with chondrocyte cells in the conditions used in the tests. In summary, the complementary nature of isosorbide derivatives with MCRs and metathesis chemistry is utilized to illustrate the potential utility of isosorbide as a building block for polymers with prospective biomedical application (namely, as novel cartilage materials)
Synthesis and Characterization of Novel IsosorbideâBased Polyester Derivatives Decorated with α âAcyloxy Amides
The synergy of multicomponent reactions (MCRs) and metathesis chemistry is applied for the synthesis of bio-based functional isosorbide polymers (i.e., polyesters) decorated with α-acyloxy amide motif. The chemical structure of the polyesters that are not accessible by any other conventional methodologies is characterized in-depth via nuclear magnetic resonance, size-exclusion chromatography, and attenuated total reflectance infrared spectroscopy. It is also observed that the âbiomass-derivedâ carbon % of the polymers varied between 66.2 and 76.9. Moreover, the thermal properties of the novel isosorbide-based polymers are investigated via thermogravimetric analysis and differential scanning calorimetry, revealing that the polymers are in the amorphous state, identified by the glass transition temperature (T) values below the human body temperature. The mechanical properties and the biocompatibility of the functional novel polyester derivative with the highest âbiomass-derivedâ carbon % are evaluated via dynamic mechanical analysis and cytotoxicity test. The exemplary polymer is biocompatible with chondrocyte cells in the conditions used in the tests. In summary, the complementary nature of isosorbide derivatives with MCRs and metathesis chemistry is utilized to illustrate the potential utility of isosorbide as a building block for polymers with prospective biomedical application (namely, as novel cartilage materials)
Resinic acid and lignin derivative dimers : new precursors for the synthesis of biobased polymers
Ces travaux de thĂšse traitent de lâutilisation dâune molĂ©cule polycyclique, lâacide abiĂ©tique, issu de la colophane, et de dĂ©rivĂ©s phĂ©noliques potentiellement dĂ©rivĂ©s de la lignine, pour la synthĂšse de polymĂšres rigides bio-sourcĂ©s. Dans les deux cas, des monomĂšres symĂ©triques et difonctionnels sont Ă©laborĂ©s par rĂ©action de dimĂ©risation des prĂ©curseurs bio-sourcĂ©s puis testĂ©s en polymĂ©risation. Dâune part, les dimĂšres de lâacide abiĂ©tique obtenus par un mĂ©canisme cationique possĂšdent des structures mal dĂ©finies qui compliquent leur polymĂ©risation. Ces dimĂšres ont alors Ă©tĂ© estĂ©rifiĂ©s avec de lâundĂ©cĂ©nol afin dâobtenir un composĂ© bis-insaturĂ© qui est ensuite polymĂ©risĂ© par ADMET. Dâautre part, un procĂ©dĂ© de dimĂ©risation de molĂ©cules phĂ©noliques, potentiellement issues de la lignine, a Ă©tĂ© dĂ©veloppĂ© par voie enzymatique utilisant une laccase. Lâavantage majeur de ce procĂ©dĂ© âvertâ rĂ©side dans la sĂ©paration trĂšs simple entre le monomĂšre, soluble, et son dimĂšre, insoluble. Ces dimĂšres ont ensuite Ă©tĂ© modifiĂ©s chimiquement afin de constituer une bio-plateforme de composĂ©s biphĂ©nyles fonctionnels. Ces composĂ©s ont Ă©tĂ© utilisĂ©s pour la synthĂšse de polyesters, polyamides et rĂ©sines Ă©poxy qui prĂ©sentent des propriĂ©tĂ©s thermiques et thermomĂ©caniques remarquables.The aim of this thesis is to investigate new biobased rigid synthons for the synthesis of polymers with high thermomechanical properties. A polycyclic biobased molecule, i.e resinic acids, and phenolic compounds potentially derived from lignin, such as vanillin were selected. Both classes of substrates were dimerized in order to get difunctional symmetric synthons. On the one hand, abietic acid dimers synthesized via a cationic mechanism presented an ill-defined structure. To avoid reactivity issues, dimers with reactive terminal double bonds were successfully synthesized by esterification of abietic acid dimers with undecenol and polymerized by ADMET methodology. On the other hand, we developed a âgreenâ process to dimerize phenolic compounds derived from lignin in large quantity and high yield via enzymatic catalysis using a laccase. The main advantage of this method is that the phenolic monomer is soluble in the reaction medium while the dimer precipitates. After chemical modifications of the dimers, we built a functional bio-platform of biphenyl derivatives. The latter were then used for the synthesis of polyesters, polyamides and epoxy resins which exhibited remarkable thermal and thermomechanical properties
Resinic acid and lignin derivative dimers : new precursors for the synthesis of biobased polymers
Ces travaux de thĂšse traitent de lâutilisation dâune molĂ©cule polycyclique, lâacide abiĂ©tique, issu de la colophane, et de dĂ©rivĂ©s phĂ©noliques potentiellement dĂ©rivĂ©s de la lignine, pour la synthĂšse de polymĂšres rigides bio-sourcĂ©s. Dans les deux cas, des monomĂšres symĂ©triques et difonctionnels sont Ă©laborĂ©s par rĂ©action de dimĂ©risation des prĂ©curseurs bio-sourcĂ©s puis testĂ©s en polymĂ©risation. Dâune part, les dimĂšres de lâacide abiĂ©tique obtenus par un mĂ©canisme cationique possĂšdent des structures mal dĂ©finies qui compliquent leur polymĂ©risation. Ces dimĂšres ont alors Ă©tĂ© estĂ©rifiĂ©s avec de lâundĂ©cĂ©nol afin dâobtenir un composĂ© bis-insaturĂ© qui est ensuite polymĂ©risĂ© par ADMET. Dâautre part, un procĂ©dĂ© de dimĂ©risation de molĂ©cules phĂ©noliques, potentiellement issues de la lignine, a Ă©tĂ© dĂ©veloppĂ© par voie enzymatique utilisant une laccase. Lâavantage majeur de ce procĂ©dĂ© âvertâ rĂ©side dans la sĂ©paration trĂšs simple entre le monomĂšre, soluble, et son dimĂšre, insoluble. Ces dimĂšres ont ensuite Ă©tĂ© modifiĂ©s chimiquement afin de constituer une bio-plateforme de composĂ©s biphĂ©nyles fonctionnels. Ces composĂ©s ont Ă©tĂ© utilisĂ©s pour la synthĂšse de polyesters, polyamides et rĂ©sines Ă©poxy qui prĂ©sentent des propriĂ©tĂ©s thermiques et thermomĂ©caniques remarquables.The aim of this thesis is to investigate new biobased rigid synthons for the synthesis of polymers with high thermomechanical properties. A polycyclic biobased molecule, i.e resinic acids, and phenolic compounds potentially derived from lignin, such as vanillin were selected. Both classes of substrates were dimerized in order to get difunctional symmetric synthons. On the one hand, abietic acid dimers synthesized via a cationic mechanism presented an ill-defined structure. To avoid reactivity issues, dimers with reactive terminal double bonds were successfully synthesized by esterification of abietic acid dimers with undecenol and polymerized by ADMET methodology. On the other hand, we developed a âgreenâ process to dimerize phenolic compounds derived from lignin in large quantity and high yield via enzymatic catalysis using a laccase. The main advantage of this method is that the phenolic monomer is soluble in the reaction medium while the dimer precipitates. After chemical modifications of the dimers, we built a functional bio-platform of biphenyl derivatives. The latter were then used for the synthesis of polyesters, polyamides and epoxy resins which exhibited remarkable thermal and thermomechanical properties
Sustainable Synthetic Approaches for the Preparation of Plant Oil-Based Thermosets
International audienc
Resinic acid and lignin derivative dimers : new precursors for the synthesis of biobased polymers
Ces travaux de thĂšse traitent de lâutilisation dâune molĂ©cule polycyclique, lâacide abiĂ©tique, issu de la colophane, et de dĂ©rivĂ©s phĂ©noliques potentiellement dĂ©rivĂ©s de la lignine, pour la synthĂšse de polymĂšres rigides bio-sourcĂ©s. Dans les deux cas, des monomĂšres symĂ©triques et difonctionnels sont Ă©laborĂ©s par rĂ©action de dimĂ©risation des prĂ©curseurs bio-sourcĂ©s puis testĂ©s en polymĂ©risation. Dâune part, les dimĂšres de lâacide abiĂ©tique obtenus par un mĂ©canisme cationique possĂšdent des structures mal dĂ©finies qui compliquent leur polymĂ©risation. Ces dimĂšres ont alors Ă©tĂ© estĂ©rifiĂ©s avec de lâundĂ©cĂ©nol afin dâobtenir un composĂ© bis-insaturĂ© qui est ensuite polymĂ©risĂ© par ADMET. Dâautre part, un procĂ©dĂ© de dimĂ©risation de molĂ©cules phĂ©noliques, potentiellement issues de la lignine, a Ă©tĂ© dĂ©veloppĂ© par voie enzymatique utilisant une laccase. Lâavantage majeur de ce procĂ©dĂ© âvertâ rĂ©side dans la sĂ©paration trĂšs simple entre le monomĂšre, soluble, et son dimĂšre, insoluble. Ces dimĂšres ont ensuite Ă©tĂ© modifiĂ©s chimiquement afin de constituer une bio-plateforme de composĂ©s biphĂ©nyles fonctionnels. Ces composĂ©s ont Ă©tĂ© utilisĂ©s pour la synthĂšse de polyesters, polyamides et rĂ©sines Ă©poxy qui prĂ©sentent des propriĂ©tĂ©s thermiques et thermomĂ©caniques remarquables.The aim of this thesis is to investigate new biobased rigid synthons for the synthesis of polymers with high thermomechanical properties. A polycyclic biobased molecule, i.e resinic acids, and phenolic compounds potentially derived from lignin, such as vanillin were selected. Both classes of substrates were dimerized in order to get difunctional symmetric synthons. On the one hand, abietic acid dimers synthesized via a cationic mechanism presented an ill-defined structure. To avoid reactivity issues, dimers with reactive terminal double bonds were successfully synthesized by esterification of abietic acid dimers with undecenol and polymerized by ADMET methodology. On the other hand, we developed a âgreenâ process to dimerize phenolic compounds derived from lignin in large quantity and high yield via enzymatic catalysis using a laccase. The main advantage of this method is that the phenolic monomer is soluble in the reaction medium while the dimer precipitates. After chemical modifications of the dimers, we built a functional bio-platform of biphenyl derivatives. The latter were then used for the synthesis of polyesters, polyamides and epoxy resins which exhibited remarkable thermal and thermomechanical properties