en fr Cycloalkenyl macromonomers from new multifunctional inimers : a platform for graft, bottle-brush and mikto-arm star copolymers Macromonomères cycloalcéniques synthétisés à partir dinimers multifonctionnels originaux : Reportar como inadecuado




en fr Cycloalkenyl macromonomers from new multifunctional inimers : a platform for graft, bottle-brush and mikto-arm star copolymers Macromonomères cycloalcéniques synthétisés à partir dinimers multifonctionnels originaux : - Descarga este documento en PDF. Documentación en PDF para descargar gratis. Disponible también para leer online.

1 IMMM - Institut des molécules et des matériaux du Mans

Abstract : The objective of the present thesis was the preparation of complex macromolecules by the combination of controlled-livingpolymerization methods such as ring-opening metathesis polymerization ROMP and highly efficient orthogonal chemistries: copper-catalyzed azide-alkyne coupling CuAAC and thiol-ene reactions.In the first part of this work, a series of well-defined structural copolymers containing a cycloolefin norbornene NB oroxanorbornene ONB functionality bearing two polymer chains including polyε-caprolactone PCL and-or polyethylene oxide PEO have been successfully prepared using the combination of ring-opening polymerization ROP and CuAAC ‘click’ chemistry. Well-defined oxanorbornenyl-functionalized bis-PCL polymers with PCL chain ranging from 1400 to 5000 g-mol were obtained by organocatalyst-mediated ROP. Norbornenyl-functionalized PEO-b-PCL block copolymers with PCL block in the range 1100 to 4100 g-mol were synthesized from commercially available PEO 2000 g-mol by CuAAC followed by ROP of CL. The presence of a hydrophilic PEO chain and a hydrophobic PCL chain in norbornenylfunctionalizedPEO-b-PCL copolymers gives rise to self-assembling properties in water solution. Critical micellar concentrations CMCare in the range of 0.08 – 0.006 g-L for copolymers with PCL chain length ranging from 10 to 36 CL units, respectively. Thecorresponding micelles show hydrodynamic diameters in range of 10 – 23 nm with low polydispersities.In the second part of this work, well-defined copolymers were used to prepare bottle-brush and mikto-arm star copolymersthrough reactions involving the cycloolefin functionality. On the one hand, high density grafting bottle-brush copolymerspolyoxanorbornene-g-bisPCL, polynorbornene-g-PEO-PCL PNB-g-PEO-PCL and PNB-b-PNB-g-PEO-PCL were achieved by ROMP according to the ‘grafting through’ strategy using Grubbs’ catalysts. On the other hand, PCL, PEO, PNIPAM-based 3-arms star, 4-arms star copolymers were obtained via radical thiol-ene reactions as demonstrated by 1H NMR, SEC and MALDI-ToF MS analysis.The high reactivity of these copolymers toward ROMP and thiol-ene reactions makes them interesting candidates in order toprepare new well-defined copolymers with controlled structures and properties through highly efficient synthetic strategies.

Résumé : Le sujet de cette thèse concerne l-élaboration de macromonomères, de copolymères greffés et de polymères étoiles de type -mikto-arm-. De telles architectures macromoléculaires ont été synthétisées par la combinaison de techniques de polymérisation contrôlées-vivantes telles que la polymérisation par ouverture de cycle par métathèse ROMP etde chimie -click- orthogonales : cycloaddition 1,3-dipolaireazoturealcyne catalysée au cuivre CuAAC et thiol-ène.Dans un premier temps, des macromonomères originaux à fonctionnalité polymérisable oxanorbornène portant deux chaînes macromoléculaires polye-caprolactone PCL et-ou polyoxyde d-éthylène POE ont été synthétisés par combinaison ROP-CuAAC. Les macromonomères à fonctionnalité oxanorbornène avec deux chaînes PCL de masse molaire moyenne en nombre Mn compris entre 1400 et 5000 g-mol ont été obtenus par ROP organocatalysée. La synthèse des macromonomères POE44-b-PCLn à fonctionnalité norbornène avec un bloc PCL de longueur variable 1100 g-mol



Autor: Duc Anh Nguyen -

Fuente: https://hal.archives-ouvertes.fr/



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