Renewable α,ω-diene monomers have been prepared from ferulic acid, biosourced diols (isosorbide and butanediol) and bromo-alkenes using a chemo-enzymatic synthetic pathway then studied as monomers in ADMET polymerization. All monomers and polymers have been thoroughly characterized using NMR, GPC, DSC and TGA. ADMET polymerization was optimized with regard to the catalyst loading (Hoveyda-Grubbs II), the reaction medium (in mass vs. in solvent), and the temperature, and led to polymers with molecular weight up to 25 kDa. Thermal analysis of these new poly(ester-alkenamer)s showed excellent thermal stabilities (283-370 °C) and tunable T g depending on the nature of the biobased diol and the chain length of the alkene in the α,ω-diene monomer.

No abstract

Transvinylation of aromatic and aliphatic diacids with vinyl acetate using several catalytic systems have been studied under conventional heating and microwave activation. In any case, a single addition of catalyst gave only low conversion into diester, due to a rapid deactivation of the catalysts, the best results being obtained with [pyridine] 2 ·Pd(OAc) 2 . Successive additions of Pd(OAc) 2 as catalyst gave better results with a 65% yield in isolated pure divinyl dodecanedioate after the successive addition of three catalyst portions. Kinetics and catalytic mechanism considerations helped to discuss these results.